Electrochemical Non-Enzymatic Glucose Sensor based on ...

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379 J. Sensor Sci. & Tech. Vol. 26, No. 6, 2017 Journal of Sensor Science and Technology Vol. 26, No. 6 (2017) pp. 379-385 http://dx.doi.org/10.5369/JSST.2017.26.6.379 pISSN 1225-5475/eISSN 2093-7563 Electrochemical Non-Enzymatic Glucose Sensor based on Hexagonal Boron Nitride with Metal–Organic Framework Composite Suresh Ranganethan 1 , Sang-Mae Lee 2 , Jaewon Lee 3 , and Seung-Cheol Chang 4+ Abstract In this study, an amperometric non-enzymatic glucose sensor was developed on the surface of a glassy carbon electrode by simply drop-casting the synthesized homogeneous suspension of hexagonal boron nitride (h-BN) nanosheets with a cop- per metal−organic framework (Cu-MOF) composite. Comprehensive analytical methods, including field-emission scanning electron microscopy (FE-SEM), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), cyclic vol- tammetry, electrochemical impedance spectroscopy, and amperometry, were used to investigate the surface and elec- trochemical characteristics of the h-BN–Cu-MOF composite. The FE-SEM, FT-IR, and XRD results showed that the h-BN– Cu-MOF composite was formed successfully and exhibited a good porous structure. The electrochemical results showed a sensor sensitivity of 18.1 µAµM -1 cm -2 with a dynamic linearity range of 10−900 µM glucose and a detection limit of 5.5 µM glucose with a rapid turnaround time (less than 2 min). Additionally, the developed sensor exhibited satisfactory anti- interference ability against dopamine, ascorbic acid, uric acid, urea, and nitrate, and thus, can be applied to the design and development of non-enzymatic glucose sensors. Keywords: Hexagonal boron nitride, copper metal–organic framework, non-enzymatic, electrochemical, glucose sensor 1. INTRODUCTION Since the first introduction of a glucose biosensor by Clark in 1962 [1], numerous glucose sensors have been developed using immobilized enzymes modified with various functional materials [2]. However, the sensors developed with modified enzymes are expensive and suffer from chloride ion poisoning and adsorption of enzyme reaction intermediates [3]. To overcome these limitations, during the last two decades, non-enzymatic biosensors have been widely developed using various nanomaterials such as metal nanoparticles, carbon nanotubes (CNTs), and graphene- based nanomaterials [4,5], due to their excellent electron transfer ability and significant resistance to chloride ion poisoning [6]. Besides the nanomaterials, metal–organic frameworks (MOFs) have also received significant attention because their metal ions exhibit a crystalline ordered structure, high porosity, large surface area, thermal stability, and chemical tenability [7]. Particularly, Cu-based MOFs (Cu-MOFs) have attracted significant attention in biosensor research [8] and have been used in the determination of biologically important compounds such as oxygen [9], H O [10], and dopamine [11]. Recently, a modified Cu-MOF has also been used as a non-enzymatic glucose-sensing material [12]. In addition, hexagonal boron nitride (h-BN), which is a wide- bandgap semiconductor that replaces the C-C pair in the carbon structure with an isoelectronic B-N bond, has been used in the field of biosensors [13]. Importantly, h-BN is isostructural to carbon-like materials such as graphite and CNTs, and thus, can be used as a composite material to construct biosensors. In the present study, an efficient method for synthesizing a unique homogeneous suspension of few layered h-BN nanosheets decorated with Cu-MOF (h-BN–Cu-MOF) was developed using a simple sonication technique. The synthesized suspension was then effectively modified onto a glassy carbon electrode (GCE) surface to develop a non-enzymatic glucose sensor by using a simple drop-casting method (Fig. 1). Therefore, the synergetic effect created by the modified h-BN–Cu-MOF composite is expected to improve the electro-oxidation sensitivity of glucose and enzyme- mimic selectivity. 1Graduate Department of Chemical Materials, Pusan National University, 2 Busandaehak-ro, Geumjeong-gu, Busan 46241, Korea. 2Engineering Research Center for Net Shape and Die Manufacturing, Pusan National University, 2 Busandaehak-ro, Geumjeong-gu, Busan 46241, Korea. 3College of Pharmacy, Molecular Inflammation Research Center for Aging Intervention, Pusan National University, 2 Busandaehak-ro, Geumjeong-gu, Busan 46241, Korea. 4Institute of BioPhysio Sensor Technology, Pusan National University, 2 Busandaehak-ro, Geumjeong-gu, Busan 46241, Korea. Corresponding author: [email protected] (Received: Sep. 21, 2017, Revised: Nov. 27, 2017, Accepted: Nov. 28, 2017) This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License(http://creativecommons.org/ licenses/bync/3.0 ) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

Transcript of Electrochemical Non-Enzymatic Glucose Sensor based on ...

379 J. Sensor Sci. & Tech. Vol. 26, No. 6, 2017

Journal of Sensor Science and Technology

Vol. 26, No. 6 (2017) pp. 379-385

http://dx.doi.org/10.5369/JSST.2017.26.6.379

pISSN 1225-5475/eISSN 2093-7563

Electrochemical Non-Enzymatic Glucose Sensor based on Hexagonal Boron Nitride

with Metal–Organic Framework Composite

Suresh Ranganethan1, Sang-Mae Lee

2, Jaewon Lee

3, and Seung-Cheol Chang

4+

Abstract

In this study, an amperometric non-enzymatic glucose sensor was developed on the surface of a glassy carbon electrode

by simply drop-casting the synthesized homogeneous suspension of hexagonal boron nitride (h-BN) nanosheets with a cop-

per metal−organic framework (Cu-MOF) composite. Comprehensive analytical methods, including field-emission scanning

electron microscopy (FE-SEM), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), cyclic vol-

tammetry, electrochemical impedance spectroscopy, and amperometry, were used to investigate the surface and elec-

trochemical characteristics of the h-BN–Cu-MOF composite. The FE-SEM, FT-IR, and XRD results showed that the h-BN–

Cu-MOF composite was formed successfully and exhibited a good porous structure. The electrochemical results showed a

sensor sensitivity of 18.1 µAµM−1cm−2 with a dynamic linearity range of 10−900 µM glucose and a detection limit of 5.5

µM glucose with a rapid turnaround time (less than 2 min). Additionally, the developed sensor exhibited satisfactory anti-

interference ability against dopamine, ascorbic acid, uric acid, urea, and nitrate, and thus, can be applied to the design and

development of non-enzymatic glucose sensors.

Keywords: Hexagonal boron nitride, copper metal–organic framework, non-enzymatic, electrochemical, glucose sensor

1. INTRODUCTION

Since the first introduction of a glucose biosensor by Clark in

1962 [1], numerous glucose sensors have been developed using

immobilized enzymes modified with various functional materials

[2]. However, the sensors developed with modified enzymes are

expensive and suffer from chloride ion poisoning and adsorption

of enzyme reaction intermediates [3]. To overcome these

limitations, during the last two decades, non-enzymatic biosensors

have been widely developed using various nanomaterials such as

metal nanoparticles, carbon nanotubes (CNTs), and graphene-

based nanomaterials [4,5], due to their excellent electron transfer

ability and significant resistance to chloride ion poisoning [6].

Besides the nanomaterials, metal–organic frameworks (MOFs)

have also received significant attention because their metal ions

exhibit a crystalline ordered structure, high porosity, large surface

area, thermal stability, and chemical tenability [7]. Particularly,

Cu-based MOFs (Cu-MOFs) have attracted significant attention in

biosensor research [8] and have been used in the determination of

biologically important compounds such as oxygen [9], H2O2 [10],

and dopamine [11]. Recently, a modified Cu-MOF has also been

used as a non-enzymatic glucose-sensing material [12]. In

addition, hexagonal boron nitride (h-BN), which is a wide-

bandgap semiconductor that replaces the C-C pair in the carbon

structure with an isoelectronic B-N bond, has been used in the

field of biosensors [13]. Importantly, h-BN is isostructural to

carbon-like materials such as graphite and CNTs, and thus, can be

used as a composite material to construct biosensors.

In the present study, an efficient method for synthesizing a

unique homogeneous suspension of few layered h-BN nanosheets

decorated with Cu-MOF (h-BN–Cu-MOF) was developed using a

simple sonication technique. The synthesized suspension was then

effectively modified onto a glassy carbon electrode (GCE) surface

to develop a non-enzymatic glucose sensor by using a simple

drop-casting method (Fig. 1). Therefore, the synergetic effect

created by the modified h-BN–Cu-MOF composite is expected to

improve the electro-oxidation sensitivity of glucose and enzyme-

mimic selectivity.

1Graduate Department of Chemical Materials, Pusan National University, 2

Busandaehak-ro, Geumjeong-gu, Busan 46241, Korea.

2Engineering Research Center for Net Shape and Die Manufacturing, Pusan

National University, 2 Busandaehak-ro, Geumjeong-gu, Busan 46241, Korea.

3College of Pharmacy, Molecular Inflammation Research Center for Aging

Intervention, Pusan National University, 2 Busandaehak-ro, Geumjeong-gu,

Busan 46241, Korea.

4Institute of BioPhysio Sensor Technology, Pusan National University, 2

Busandaehak-ro, Geumjeong-gu, Busan 46241, Korea.+Corresponding author: [email protected]

(Received: Sep. 21, 2017, Revised: Nov. 27, 2017, Accepted: Nov. 28, 2017)

This is an Open Access article distributed under the terms of the Creative

Commons Attribution Non-Commercial License(http://creativecommons.org/

licenses/bync/3.0) which permits unrestricted non-commercial use, distribution,

and reproduction in any medium, provided the original work is properly cited.

Suresh Ranganethan, Sang-Mae Lee, Jaewon Lee, and Seung-Cheol Chang

J. Sensor Sci. & Tech. Vol. 26, No. 6, 2017 380

2. EXPERIMENTAL

2.1 Materials and Chemicals

D-Glucose, ascorbic acid (AA), acetaminophen, uric acid (UA),

dopamine, NaOH, NaCl, copper nitrate trihydrate (Cu(NO3)2.3H2O),

1,3,5-benzenetricarboxylic acid (H3BTC), and dimethylformamide

(DMF) were purchased from Sigma-Aldrich (USA). h-BN mesh

powder (particle size: 1−5 μM) was purchased from Alpha Easer Co.

(Japan). All other reagents, of analytical grade, were purchased from

Sigma-Aldrich (USA) and used without further purification. All

aqueous solutions were prepared using deionized water (Milli-Q

water purifying system, 18 MΩ·cm−1).

2.2 Instrumentation

Cyclic voltammetry (CV) and amperometry were performed using

an electrochemical workstation (CompactStat, Ivium Technologies,

the Netherlands) with a conventional three-electrode cell system

consisting of a GCE (3 mm in diameter), a Ag/AgCl reference

electrode, and a platinum-wire auxiliary electrode. CV was carried out

in a NaOH solution by potential sweeping from +0.2 to +0.8 V, at a

scan rate of 50 mVs−1. For amperometry, the developed sensor was

inserted into an electrochemical cell, to which a 990 µL aliquot of

NaOH solution was added. The cell was then set and the sensor was

polarized at a potential of 0.60 V. After achieving a stable baseline

response with NaOH, a 10 µL aliquot of glucose sample was added,

and the current responses as a function of time were recorded. The

amperometry measurements were repeated to perform calibration and

investigate the sensor reproducibility and storage stability.

Electrochemical impedance spectroscopy (EIS) was performed

using an electrochemical workstation (VersaSTAT, Princeton Applied

Research, USA) in the frequency range of 100 KHz to 0.1 Hz at a DC

potential of 250 mV and AC potential of ±5 mV. To investigate the

surface characteristics, field-emission scanning electron microscopy

(FE-SEM), X-ray diffraction (XRD), and Fourier-transform infrared

spectroscopy (FT-IR) were carried out using the sensors modified

onto iridium tin oxide electrodes. FE-SEM was performed using a

field-emission scanning electron microscope (Hitachi S-4200, Japan)

operated at 15 kV, 150 W, and powder XRD patterns were collected

on an X-ray D/max-2200vpc (Rigaku Corporation, Japan) instrument

operated at 40 kV and 20 mA using Cu kα radiation (K = 0.15406).

2.3 h-BN–Cu-MOF-modified sensor preparation

The hydroxyl-functionalized aqueous dispersion of a few layers of

h-BN nanosheets was synthesized using the sonication-centrifugation

process [14]; 20 mg of the h-BN powder was dispersed in 10 mL of

deionized water and sonicated for 8 h, and the dispersion was

centrifuged at 3500 rpm for 12 min and filtered. The filtrate was then

collected as a “homogeneous” aqueous dispersion of a few layers of

h-BN nanosheets.

Cu-MOF was synthesized using a previously reported thermal

method [11, 15]; 0.55 g of Cu(NO3)2·3H2O was dissolved in 40 mL

of deionized water and mixed with 80 mL of 37.5 mM H3BTC

prepared in a 1:1 mixed solution of DMF and ethanol. The mixture

was kept in a water bath at 85°C for 24 h, and the blue powder of Cu-

MOF was separated by filtration and then dried at 80°C for 8 h. A

bare GCE was polished using 0.3-µm alumina slurries and sonicated

in ethanol for 10 min. After sonication, the GCE was rinsed

thoroughly with distilled water and dried at ambient temperature. To

prepare the h-BN–Cu-MOF composite, 3.0 mgmL−1 of the Cu-MOF

was dispersed in 1 mL of the h-BN dispersion under stirring for 10

min. A 5 μL aliquot of the composite suspension was drop-casted

onto the GCE surface and dried under ambient conditions.

Additionally, a 2 μL aliquot of Nafion solution (1.0 wt.% in ethanol)

was drop-cased to entrap the h-BN–Cu-MOF composite, which was

modified on the GCE. The constructed sensor is denoted as GCE–h-

BN–Cu-MOF/NF.

3. RESULTS AND DISCUSSIONS

3.1 Surface characteristics of h-BN–Cu-MOF composite

XRD was performed to study the structures of Cu-MOF without h-

BN and the h-BN–Cu-MOF composite (Fig. 2(A)). The XRD peaks

of Cu-MOF revealed its crystalline nature [16,17]; h-BN–Cu-MOF

spectra exhibited a diffraction peak at 26.31° for the (002) plane, and

at 42.93°, 44.16°, and 55.20° for the (100), (101), and (104) planes,

respectively. These spectra confirmed the formation of the h-BN–Cu-

MOF composite [18]. Fig. 2(B) shows the FT-IR spectra of Cu-MOF

and the h-BN–Cu-MOF composite. The FT-IR spectra of Cu-MOF

exhibit six prismatic crystals with Cu atoms, involving two carboxylic

Fig. 1. Illustration of proposed h-BN–Cu-MOF composite modified

non-enzymatic glucose sensor.

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381 J. Sensor Sci. & Tech. Vol. 26, No. 6, 2017

“O” atoms, three water molecules, and a broad-band peak observed at

3432 cm-1, and conform to the O-H group in Cu-MOF [19,20].

However, the FT-IR spectra of the h-BN–Cu-MOF composite clearly

shows that the peak intensity of the O-H group and organic ligand

(BTC)2 C-O-C peak at 1110 cm-1 are completely diminished as

compared to case of pure Cu-MOF. The in-plane B-N transverse

stretching vibration peak at 1375 cm-1 and the out-of-plane B-N-B

bending vibration peak at 816 cm-1 can be suggested as a fingerprint

of sp2 bonds in h-BN sheets [21]. These results confirm that Cu-MOF

is effectively attached to h-BN sheets through the non-covalent

interaction induced by the sonication technique developed. The FE-

SEM image of pure Cu-MOF (Fig. 2(C)) shows crystals in micron-

sized tubular shape [22], while that of the h-BN–Cu-MOF composite

(Fig. 2(D)) shows a strong interaction of Cu-MOF with the h-BN

sheets. The Fe-SEM images clearly indicate that the h-BN sheets are

well-ordered in 2D form and are micron-sized.

3.2 Electrocatalytic oxidation of glucose

To investigate the electrocatalytic activity of the GCE–h-BN–Cu-

MOF/NF sensor, CV measurements were carried out in 0.15 M

NaOH at a scan rate of 50 mVs−1 with four prepared sensors: bare

GCE, GCE–h-BN/NF, GCE–Cu-MOF/NF, and GCE–h-BN–Cu-

MOF/NF. As shown in Fig. 3(A), in the absence of glucose, the

oxidation current in GCE–h-BN–Cu-MOF/NF is higher than that in

the other modified sensors, which can be attributed to the Cu (II)/Cu

(III) redox couple and the water-splitting process [23]. In the presence

of 0.3 mM glucose in 0.15 M NaOH, a clear glucose oxidation peak

appears at +0.60 V on GCE–h-BN–Cu-MOF/NF (inset in Fig. 3(A)).

However, the bare GCE, GCE–h-BN/NF, and GCE–Cu-MOF/NF

sensors show no detectable oxidation peaks of glucose. As illustrated

in Fig. 1, the electrocatalytic oxidation of glucose on GCE–h-BN–Cu-

MOF/NF underwent several steps: first, Cu-MOF was electrochemically

oxidized to Cu (III) species such as CuOOH [24], and then, glucose

was catalytically oxidized by Cu (III) species to form gluconic acid,

and at the same time, Cu (III) species were reduced to Cu (II) [25].

Fig. 2. (A) XRD images and (B) FT-IR spectra of the Cu-MOF and

the h-BN-Cu-MOF composite, (C) FE-SEM image of Cu-

MOF, and (D) FE-SEM image of the h-BN-Cu-MOF com-

posite.

Fig. 3. (A) Cyclic voltammograms of GCE-bare, GCE-h-BN/NF,

GCE-Cu-MOF/NF, and GCE-h-BN Cu-MOF/NF sensors in

the absence of glucose and in the presence of 0.3 mM glucose

(Inset). (B) EIS of GCE-bare, GCE-h-BN/NF, GCE-Cu-

MOF/NF, and GCE-h-BN-Cu-MOF/NF sensors in 0.1 M KCl

solution.

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Suresh Ranganethan, Sang-Mae Lee, Jaewon Lee, and Seung-Cheol Chang

J. Sensor Sci. & Tech. Vol. 26, No. 6, 2017 382

The four differently modified sensors were also employed for the

EIS study, as described in Section 2.2, and the Nyquist plot of each

sensor was obtained as shown in Fig. 3(B). It is well known that, in

EIS, the semicircle formed at a high-frequency region is related to the

charge transfer-limited process of the interface, while the linear

response formed at a low-frequency region is related to the diffusion-

limited process [26]. These results reveal that the oxidation peak at

+0.60 V shows a strong electrocatalytic activity of GCE–h-BN–Cu-

MOF/NF and a negligible charge transfer resistance of all sensors. It

is, therefore, suggested that the enhancement of electrocatalytic

activity is caused by the effective diffusion control process, the larger

size of the active surface area, and the high electron transfer rate of

the GCE–h-BN–Cu-MOF/NF sensor

In the mechanism of non-enzymatic glucose sensing, the

electrochemical behavior of Cu (II) and Cu (III) redox couple can be

considered as an essential factor for glucose oxidation at the sensor

surface [27,28]. The enhanced performance of the GCE–h-BN–Cu-

MOF/NF sensor is attributed to this factor through comparison with

other nanosized powders [29] and nanowires on film-type glucose

sensors [30]. Due to the large surface area of the nanoporous layers

of h-BN sheets decorated with Cu-MOF with high crystal quality, the

synergetic effect of the GCE–h-BN–Cu-MOF/NF sensor can explain

the selective glucose oxidation and enhancement of the charge

transfer resistance mechanism in Cu-MOF by π-π* transition with a

few layers of h-BN sheets. This also confirms that the electrons

generated are efficiently transferred from Cu-MOF to the sensor

surface with the high driving force created by the Schottky barrier

[31].

3.3 Sensor optimization

To achieve optimum sensor performance conditions, the operating

pH and potential were investigated by CV and amperometry

measurements toward glucose sensing. The non-enzymatic oxidation

of glucose produces gluconolactone and the simultaneous oxidation

continues to dehydrogenate, which is closely related to the presence

of hydroxide ions [26]. Thus, the hydroxide ions play an important

role in the oxidation of glucose at the GCE–h-BN–Cu-MOF/NF

sensor.

Fig. 4(A) shows the cyclic voltammograms of 0.3 mM glucose

prepared in deionized water with different concentrations of NaOH

(0−0.15 M). The oxidation peak current gradually increases with

NaOH concentration and slightly shifts to the negative-potential side

due to an easy oxidation of aldehyde and hydroxyl groups in glucose.

Accordingly, 0.15 M NaOH (pH 13.0) was used as the operating

medium in all experiments. A hydrodynamic voltammogram was

constructed using GCE–h-BN–Cu-MOF/NF with 0.1 mM glucose

(Fig. 4(B)). The maximum response was obtained at a potential of

+0.60 V and the signal response decreased dramatically beyond this

potential. Accordingly, +0.60 V was used as the operating potential in

all experiments.

3.4 Amperometric sensor calibration for glucose

Amperometry measurements were performed using the developed

sensors by adding glucose samples, as described in Sections 2.2 and

3.2. The current responses obtained using the bare GCE and GCE–h-

BN/NF sensors were negligible after the addition of glucose. As

shown in Fig. 5(A), in contrast, stable and immediate current

responses were observed after the addition of glucose and calibration

curves for glucose were constructed using the GCE–Cu-MOF/NF and

GCE–h-BN–Cu-MOF/NF sensors. As seen in Fig. 5(B), the current

responses reached steady-state values in less than 5 s. In the curve for

the GCE–Cu-MOF/NF sensor, the linear dynamic range was found to

be 10−900 μM and the sensitivity was calculated to be 11.0

μAμM−1cm−2. Responses to glucose using the GCE–h-BN–Cu-MOF/

NF sensor showed the same linearity ranges as high as 900 µM with

improved sensitivity of 18.1 μAμM−1cm−2, which was 1.5 times

higher than that of the GCE–Cu-MOF/NF sensor. The detection limit

of the GCE–h-BN–Cu-MOF/NF sensor was calculated to be 5.5 µM

and taken as six times the standard deviation of the current change

Fig. 4. (A) CVs of 0.3 mM glucose in different concentrations of

NaOH (0.0 M, 0.01 M, 0.03 M, 0.05 M, 0.08 M, 0.1 M, and

0.15 M) using the GCE-h-BN-Cu-MOF/NF sensor at a scan

rate of 50 mVs−1. (B) Effects of applied potential on the

amperometric response of the sensor to 0.1 mM glucose in

0.15 M NaOH (pH 13).

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383 J. Sensor Sci. & Tech. Vol. 26, No. 6, 2017

due to the addition of a blank solution. The results obtained, therefore,

indicate that the h-BN–Cu-MOF composite-modified sensor exhibited

the highest sensitivity to glucose and improved the amperometric

sensor performance due to the synergetic effect of the h-BN–Cu-MOF

composite, as described in Section 3.2 [32].

3.5 Sensor performance characteristics

To the best of our knowledge, there are few reports on the non-

enzymatic glucose-sensing applications of Cu-MOF composites. In

this study, the performances of non-enzymatic electrochemical

sensors modified with Cu-MOFs were studied, and are summarized in

Table 1: Cu@C800: anthill-like Cu@carbon nanocomposites;

CuFe2O4: copper ferrite; MWCT: multiwall carbon nanotube; CuO:

Nanothorn Cu foam; Cu-MOF: copper metal–organic framework;

GCE: glassy carbon electrode. The summary clearly demonstrates

that the Cu-MOF-modified sensors rever good electrocatalytic ability

and can be used as non-enzymatic glucose sensors.

Interference is one of the major limitations in verifying the

selectivity of the developed non-enzymatic glucose sensor, because

the real samples may contain some co-existing biological compounds

in human blood serum. Fig. 6 shows the signal of the biosensors

following the addition of 0.1 mM DA, AA, UA, urea, and nitrate, and

0.2 mM NaCl. There was no significant change in the signal in

response to these compounds, indicating no substantial interference in

glucose detection. In addition, the use of Nafion film, as described in

Section 2.3, could avoid the interferences from AA and UA because

of its long backbone chain with negatively charged sulfonic groups

and their ionic properties. The interfering current responses for the

added compounds were only less than 6.0% that of glucose. The

relative standard deviation as a measure of inter-electrode

reproducibility was calculated to be 3.5%. This proved good

reproducibility of the developed sensor. Furthermore, only 4% loss of

the initial sensor sensitivity was observed after five-week storage of

the sensor at 4°C in dark.

Table 1. Sensors modified with Cu-MOF composites as non-enzymatic glucose sensing applications

Modified sensor Operating potential (V) Detection limit (μM) Dynamic Linear range (mM) Ref

Cu@C800 + 0.55 29.8 0.2−8.0 [33]

GCE/CuFe2O4MWCT +0.40 0.2 0.0005−1.4 [34]

CuO nanothorna +0.50 0.276 0.0002−2 [35]

Cu-MOF +0.70 1.0 0.005−2.8 [36]

GCE–h-BN–Cu-MOF/NF +0.60 5.5 0.01−0.90 This work

Fig. 5. (A) Amperometric current responses to glucose using the dif-

ferent sensors at a potential of +0.60 V in 0.15 M NaOH:

GCE-bare, GCE-h-BN/NF, GCE-Cu-MOF/NF and GCE-h-

BN-Cu-MOF/NF sensors. (B) Calibration curves for glucose

using the GCE-Cu-MOF/NF and GCE-h-BN-Cu-MOF/NF

sensors.

Fig. 6. Amperometric response to 0.1 mM glucose, 0.1 mM DA,

AA, UA, urea, NO3

- and 0.2 M NaCl at GCE-h-BN-Cu-MOF/

NF sensor in 0.15M NaOH.

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J. Sensor Sci. & Tech. Vol. 26, No. 6, 2017 384

4. CONCLUSIONS

A new method for synthesizing a non-enzymatic glucose sensor

was developed by simply drop-casting composite suspensions. The

composite was prepared based on a Cu-MOF composite decorated

with h-BN nanosheets, by a simple sonication technique developed.

The FE-SEM, FT-IR, and powder XRD results confirmed that the

composite was formed successfully with good porous structure. The

detection limit of the GCE–h-BN–Cu-MOF/NF sensor was 5.5 μM

glucose with a linear dynamic range of 10−900 µM. The developed

sensor exhibited enhanced features of sensitivity, reproducibility,

long-term stability, and anti-interference against electroactive species

in real biological samples such as DA, AA, and UA. These results

proved the usefulness of the sensor for glucose determination. Further

research is currently underway to develop a new non-enzymatic

glucose micro-sensor platform for real biological or clinical sample

analysis.

ACKNOWLEDGMENT

This work was supported by a 2-Year Research Grant of Pusan

National University.

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