NANO EXPRESS Open Access

A new nanosensor composed of laminated

samarium borate and immobilized laccase for
phenol determination
Ping Hu, Xinlin Zhou and Qingsheng Wu
*
Abstract
A new nanosensor composed of laminated samarium borate and immobilized laccase was developed for phenol
determination. The laminated samarium borate was synthesized by a mild solid-state-hydrothermal (S-S-H) method
without any surfactant or Template. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and
scanning electron microscopy (SEM) were used to characterize the samples. The morphology of the as-prepared
materials was characterized by SEM, which shows that laminated samarium borate are uniform nanosheets with
a layer-by-layer self-assembled single-crystal structure. These laminated samarium borate have typical diameters
of 3 ~ 5 m and the thickness of each layer is in the range of 10 ~ 80 nm. And then, these SmBO
3
multilayers
were used to immobilize the laccase. The proposed nanosensor composed of laminated samarium borate and
immobilized laccase was successfully developed for phenol determination. Cyclic voltammetry were used to study
the nanosensor. The proposed nanosensor displayed high sensitivity toward phenolic compounds. The linearity of
the nanosensor for the detection of hydroquinone was obtained from 1 to 50 M with a detection limit of 3 10
7
M (based on the S/N = 3).
Keywords: SmBO
3
; Nanosheets; Laccase; Immobilization; Determination
Background
With the development of the economy, more and more
pollutants are eroding the human survival environment.
Then the detection and treatment of environmental
pollutions have aroused great attentions of scientists.
Belonging to multicopper proteins, laccases are widely
existed in nature especially fungi [1,2]. It is a phenol oxi-
dase that can catalyze oxidation of many organic pollut-
ants in water [3]. Wan and his group [4] had elaborated
the progress on the research of laccases, namely the ac-
tive center of copper ions, the three-dimensional struc-
ture of protein, and its catalytic mechanism. Substrate
specificity of laccases was exploited to remove pollutants
from the environment without creating the negative
effects associated with many other methods [5,6]. It is
well known that the enzyme is often easily inactivated
in practical applications due to complex environment
conditions, which limit its further industrial application
[7,8]. Consequently, immobilized laccases have received
much attention from researchers in recent years because
of its substantial advantages over free laccases such as
continuous reuse, easy separation of the product from
the reaction media, easy recovery of the enzyme, and
improvement in enzyme stability. Nowadays, many dif-
ferent types of methods have been employed in the
immobilization of enzymes, such as adsorption, entrap-
ment, cross-link, and covalent attachment. Recently, it is
reported that laccase has been successfully immobilized
[9-11] on many different types of supports, such as
activated carbon [3], magnetic chitosan [12], alginate
chitosan [13], porous glass [14], chitosan/poly(vinyl alco-
hol) composite nanofibrous membranes [15], cellulose-
polyamine composite [16], alginate, kaolinite, polymer
beads and membranes polystyrene microspheres, short-
range ordered aluminum hydroxide, and so on [17-20].
However, leakage, desorption, and the loss of enzyme ac-
tivity were major problems in laccase immobilization,
which was related to many factors involving the enzyme
* Correspondence: [email protected]
Department of Chemistry; Key Laboratory of Yangtze River Water
Environment, Ministry of Education, Tongji University, 1239 Siping Road,
Shanghai 200092, Peoples Republic of China
2014 Hu et al.; licensee Springer. This is an Open Access article distributed under the terms of the Creative Commons
Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction
in any medium, provided the original work is properly credited.
Hu et al. Nanoscale Research Letters 2014, 9:76
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itself, polymer matrix, reaction reagents, and process
conditions [9]. Therefore, it is of great interest in devel-
oping novel technologies on laccase immobilization to
improve catalytic activity of laccase and increase its in-
dustrial application.
Among those laccase supports, inorganic materials are
more attractive because of their regular structure, good
mechanical, chemical, and thermal stabilities [21-23].
Nanomaterials have attracted increasing attention for
their novel properties and potential applications with
small dimensions [24,25]. Inorganic nanomaterials of
rare-earth borate compounds show high vacuum ultra-
violet (VUV) transparency and exceptional optical dam-
age thresholds. Acentric lanthanide borate crystals are
useful in a wide variety of photonic devices for unique
optical, nonlinear optical, laser, electronic, and other
physical properties [24,25]. In the past decades, the rare-
earth borates are widely used in many fields [26-30] and
a number of synthetic methods have been employed to
fabricate them. However, many routes suffer from the
use of high temperature, tedious processes, and environ-
mental pollution. Therefore, it is still an attractive and
necessary topic for the development of environmentally
friendly, facile, and reproducible methods to fabricate
rare-earth borate nanometer materials.
In this paper, we choose a novel laminated SmBO
3
multilayer as support for the immobilization of laccase.
The SmBO
3
multilayer samples were synthesized via the
solid-state-hydrothermal (S-S-H) method, which exhibits
many advantages, such as no side products, facile oper-
ation, and low cost. Then laccase was immobilized in
SmBO
3
nanosheets for the fabrication of the nanosensor.
The performance of the proposed nanosensor composed
of the laminated samarium borate and immobilized lac-
case in the catalytic determination of phenolic com-
pounds has been investigated in detail.
Methods
Reagents and apparatus
All reagents were analytical grade in the synthesis sys-
tem. H
3
BO
3
(>99.0%), Sm
2
O
3
(>99.99%), Na
2
HPO
4

12H
2
O (>99.0%), C
6
H
8
O
7
H
2
O (>99.8%), hydroquinone
(>99.99%), and 2, 6-dimethoxyphenol (>99.99%) were
purchased from Shanghai Chemical Reagent Co, Ltd.
(Shanghai, China) and used without any purification.
Laccase was provided by Shanghai Daidi Industrial De-
velopment Co, Ltd. (Shanghai, China) and stored at 4C
before using.
The morphology and structure of the samples were
inspected by using a field emission scanning electron
microscope (FE-SEM, Hitachi S4800, Tokyo, Japan) at
an accelerating voltage of 5 KV. The phase purity and
crystallinity of the samples were characterized by X-ray
powder diffraction (XRD) performed on a D8 FOCUS
diffractometer (Bruker, Madison, WI, USA) with CuK
radiation ( = 0.154056 nm), employing a scanning rate
of 0.02 s
1
, in the 2 ranges from 10 to 70. Infrared
spectra (4,000 to 400 cm
1
) are recorded by Nicolet 5DX
Fourier transform infrared spectroscopy (FTIR; Thermo
Fisher Scientific, Waltham, MA, USA) equipped with a
TGS/PE detector and a silicon beam splitter with 1 cm
1
resolution.
Electrochemical experiments were carried out with a
CHI-660B electrochemical workstation (Shanghai, China).
Measurements were performed at least three times on
a glassy carbon electrode (GCE). A conventional three-
electrode system was employed, comprising a GCE (3-mm
diameter) as the working electrode, a platinum wire as the
auxiliary electrode, and an Ag/AgCl (saturated KCl) as the
reference electrode. Voltammetric responses were re-
corded in 50 ml of substrate solutions prepared in PBS
buffer solution. First, the modified electrode was activated
by several successive voltammetric cycles from 0.20 to
0.80 V. Second, cycle voltammograms (CVs) at the rate of
50 mV s
1
were carried out from 0.20 to 0.80 V after
subtracting the background. Finally, the GCE was regener-
ated by 10 successive cyclic voltammetric sweeps in the
blank solution. After several measurements, the GCE
should be repolished. All the electrochemical measure-
ments were carried out at room temperature.
Preparation of SmBO
3
nanocrystals
Precursor-laminated SmBO
3
multilayers were synthe-
sized by solid-state-hydrothermal method. In a typical
synthesis, 0.6 mmol Sm
2
O
3
, 0.72 mmol H
3
BO
3
, 14 ml
deionized water are mixed in a 20-ml-capacity Teflon-
lined autoclave. The autoclave is sealed and maintained
at 200C constantly for 36 h and then cooled to room
temperature naturally. The precipitation is centrifuged
and washed with deionized water several times. Finally,
as-obtained products are dried under vacuum at 60C for
4 h. We propose that the formation processes of SmBO
3
in the solid-state-hydrothermal system at 200C can be
assigned to two stages: Sm
2
O
3
is first transformed into hy-
droxide, Sm(OH)
3
, then the hydroxide interacts with
H
3
BO
3
to form products. The formation reactions of
SmBO
3
are proposed and shown in Figure 1.
Immobilization of laccase on SmBO
3
nanocrystals
The SmBO
3
multilayers were employed as carriers for
the immobilization of laccase, and the laccase was
Sm
2
O
3 +
H
2
O Sm(OH)
3
(1)
Sm(OH)
3 +
H
3
BO
3
SmBO
3
(2)
Figure 1 Formation mechanism of SmBO
3
in the S-S-H route.
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immobilized on these materials by the physical adsorp-
tion method. In a typical procedure, 100 mg of SmBO
3
support was suspended in 10 ml of phosphate buffer
(pH = 7.0) containing a certain amount of laccase (about
20 mg). The mixture of the supports and laccase solu-
tion was slowly stirred at room temperature for 12 h.
Subsequently, the laccase immobilized on SmBO
3
was
separated by a centrifuge. Then the samples were washed
with 10 ml of buffer solution by shaking for 5 min
and separated quickly using a centrifuge. The washing
procedure was repeated several times until no protein was
detected in the supernatant. Finally, the laccase immobi-
lized by SmBO
3
were stored at 4C before using. The per-
centage of the immobilized laccase on the SmBO
3
samples
is in the range of 10.7%~15.2%.
Preparation of the glassy carbon electrode
Ultrasonic agitation was used to disperse 1-mg SmBO
3
-
immobilized laccase into 1-ml Nafion to give a suspen-
sion (1 mg ml
1
). Before an experiment, the GCE was
polished successively with 0.1-m -Al
2
O
3
powder, and
then on a polishing cloth. Residual polishing material
was removed from the electrode surface by ultrasonic
agitation in concentrated HNO
3
, distilled water, and
absolute ethanol. Then, the GCE was coated with 10 l
of laccase immobilized by SmBO
3
-Nafion suspension
Figure 2 Typical SEM images of as-prepared SmBO
3
(a),
corresponding high-magnified images (b), and immobilized
laccase images (c).
Figure 3 XRD pattern of SmBO
3
via S-S-H method at 200C for
36 h.
Figure 4 FTIR spectra of SmBO
3
(a), laccase (b), and SmBO
3
-
immobilized lacasse (c).
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(1 mg ml
1
) and the solvent evaporated under room
temperature for 1 h. The modified electrode was cleaned
with distilled water before use.
Results and discussion
SEM studies
Figure 2a shows SEM micrographs of as-prepared SmBO
3
multilayer obtained via the additive-free S-S-H method at
200C for 36 h. Figure 2b was the corresponding high-
magnified images. The multilayer shapes consist of multi-
layer nanosheets. These nanosheets have typical diameters
of 3 ~ 5 m while the thickness of the single layer are
in the range of 10 ~80 nm. These microparticles are
nonaggregated with narrow size distribution. The pseudo-
vaterite self-assembled SmBO
3
multilayers exhibit advan-
tages in high-ratio surface area and analogy-graphite layer
structure, which are favorable for potential application in
enzyme immobilization. Figure 2c shows that the laccase
was effectively filled among layers of SmBO
3
by physical
absorption. Inspired by this, we inferred the multilayer
structures of SmBO
3
suitable for immobilization of other
enzymes.
The XRD pattern analysis of as-prepared SmBO
3
samples
To ascertain the structure of as-prepared SmBO
3
samples,
corresponding XRD patterns of samples were investigated
and shown in Figure 3. The pattern is inconsistent with
aragonite-type, which are indexed in the standard pattern
database listed in JCPDS. To make clear the crystal struc-
ture, the MDI Jade (5.0 Edition) software was applied to
auto index the similar patterns in JCPDS. It was found
that the peak positions are in accordance with the
primitive-lattice hexagonal phase SmBO
3
(No. 13-0479).
FTIR spectra analysis
Figure 4a shows FTIR spectra of SmBO
3
prepared via
the S-S-H method at 200C for 36 h. The absorbance
peaks are assigned to the vibration mode of the ring
anion B
3
O
9
9
. A feature of this model is that the B
3
O
9
9
group is involving a planar ring with D3 symmetry. The
assignment model is proposed in hexagonal LnBO
3
as
follows: Due to the stretching vibrations of the ring
sketch of the cyclic trimeric ion and the terminal B-O
and bending vibrations of them, the absorption bands in
the region of 800 to 1,200 cm
1
and below 500 cm
1
, re-
spectively [31-34]. To investigate the binding between
the laccase and the laminated SmBO
3
multilayers, FTIR
spectra for the laminated SmBO
3
multilayers, lacasse,
and laminated SmBO
3
multilayers with immobilized lac-
case were measured.
Figure 4b,c shows the FTIR spectra laccase and SmBO
3
-
immobilized lacasse. Compared to the typical absorption
peaks of lacasse at 3,401, 2,923, and 1,649 cm
1
and the
main absorption peaks of SmBO
3
at 1,110, 960, 894, and
827 cm
1
, the absorption of SmBO
3
-immobilized lacasse
include all of the above peaks. So it is evident that the lac-
case was successfully immobilized on SmBO
3
nanosheets.
Moreover, it can be seen from Figure 4 that the positions
of lacasse and those immobilized in SmBO
3
are nearly at
Figure 5 Scheme of reactions occurring at surface of laccase-
immobilized SmBO
3
-modified GCE.
Figure 6 Cyclic voltammetry of SmBO
3
-immobilized laccase (a)
and bare electrode (b). At a scan rate of 50 mV/s in pH 4.0 PBS, at
room temperature with the presence of 5 10
5
mol l
1
hydroquinone.
Figure 7 Influence of pH on anodic peak potentials of laccase
immobilized on SmBO
3
. At a scan rate of 50 mV s
1
in presence
of 5 10
5
mol l
1
hydroquinone, at room temperature.
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the same place, suggesting that the lacasse retains its na-
tive structure in SmBO
3
-immobilized lacasse.
Electrochemical properties
The response of laccase-immobilized SmBO
3
nanosheets
for phenolic compound detection is based on the mechan-
ism in which a substrate (hydroquinone in this case), lac-
case, and oxygen are involved. The enzymatic mechanism
involved in laccase-immobilized SmBO
3
for phenolic com-
pound detection is the same as the bare laccase [4]. Lac-
case as one of the multicopper oxidases contains four
copper atoms and catalyzes the four-electron reduction of
O
2
to H
2
O at a trinuclear copper cluster. The catalytic
process consists of the oxidation of hydroquinone by
laccase followed with the reduction of O
2
by laccase
(Figure 5).
The electrochemical behaviors of laccase-immobilized
SmBO
3
-modified GCE in various solutions were studied
using cyclic voltammetry and the results are shown in
Figure 6. The laccase-immobilized SmBO
3
-modified GCE
remain its redox behaviors in pH 4.0 PBS at room
temperature with the presence of 5 10
5
mol l
1
hydro-
quinone. The anodic peak currents of laccase-immobilized
SmBO
3
-modified GCE are 3.0 A. Compared to the an-
odic peak current of bare electrode which is 1.48 A,
the anodic peak current of modified GCE is at least two
times greater. These demonstrate that the electrode of the
SmBO
3
-immobilized laccase has a better sensitivity to the
substrate. At the same time, we found that the E of laccase-
Figure 8 Influence of pH on anodic peak currents of laccase
immobilized on SmBO
3
. At a scan rate of 50 mV s
1
in presence
of 5 10
-5
mol l
1
hydroquinone, at room temperature.
Figure 9 Influence of square root of scan rate on anodic peak
currents of laccase immobilized on SmBO
3
. At a scan rate of 50
mV s
1
in pH 4.0 PBS, at room temperature in presence of 5 10
5
mol s
1
hydroquinone.
Figure 10 Calibration graphs of concentration of hydroquinone
of laccase-immobilized SmBO
3
-modified electrode. a. 5, b. 3, c. 1,
d. 0.8, e. 0.5, f. 0.3, g. 0.1, h. 0 10
5
mol l
1
.
Figure 11 Calibration curve between catalytic current and
concentration of hydroquinone in pH 4.0 PBS, at room
temperature.
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immobilized SmBO
3
-modified GCE (0.51 V) is larger than
bare electrode (0.47 V). According to the Gibbs-Helmholtz
equation G= nFE, G of the laccase-immobilized
SmBO
3
-modified GCE is smaller than the bare electrode.
These results suggest that the reaction occurs on the
laccase-immobilized SmBO
3
electrode is much easier than
the bare electrode.
Optimal parameters
We used 0.2 mol l
1
Na
2
HPO
4
12H
2
O and 0.1 mol l
1
C
6
H
8
O
7
H
2
O solutions to adjust the pH of the buffer
solutions from 3.0 to 8.0. Figures 7 and 8 show the rela-
tionship between the pH values and the anodic peak po-
tentials, the anodic peak currents from CV, respectively.
The potentials shifted negatively with increasing pH
value. At the same time, the anodic peak currents in-
creased slightly with increasing pH, and when the pH
exceeded 4.0, the anodic peak currents decreased imme-
diately. It may be due to the high oxidation potentials
and the serious interference at low pH values. Therefore,
pH 4.0 was chosen as the optimum pH in this work.
Cycle voltammograms were employed to investigate
the influence of scan rate on hydroquinone oxidation at
the laccase-immobilized SmBO
3
-modified electrode. The
results are shown in Figure 9. At scan rates in the range of
0.01 to 0.1 V s
1
, the oxidative peak currents of the
laccase-immobilized SmBO
3
-modified electrode in hydro-
quinone solution increased linearly with the square root of
the scan rate, which proved that the electro-oxidation of
hydroquinone was a diffusion-controlled process.
Calibration graphs
The anodic peak currents (I
p
) of laccase-immobilized
SmBO
3
-modified electrode of the CV are proportional
to the concentration of hydroquinone from 1 10
6
to
5 10
5
mol l
1
. The picture is shown in Figure 10.
The calibration curve under optimal conditions is
shown in Figure 11. The linear response range of laccase-
immobilized SmBO
3
-modified electrode to hydroquinone
concentration is from 1 to 50 M with a correlation coeffi-
cient of 0.998 (I = 4.13c +0.42, r = 0.998). The detection
limits of the compounds are estimated to be 3 10
7
mol l
1
.
Conclusions
In summary, we have demonstrated a nanosensor com-
posed of laminated samarium borate and immobilized
laccase for phenol determination. These SmBO
3
nano-
sheets have been successfully prepared via a mild solid-
state-hydrothermal method without any surfactant or
template, and laccase was successfully immobilized on
these multilayers through physical adsorption method.
The uniform multilayer-intersected structure could play
an important role in the adsorption of laccase. This
novel laccase immobilization method based on SmBO
3
improved the performance of the laccase for phenol
determination. The linear range and bioactivity of
laccase-modified electrode can also satisfy the practical
application. The present study has enlarged the family of
support for laccase immobilization and may provide an
efficient approach for phenol determination.
Competing interests
The authors declare that they have no competing interests.
Authors contributions
PH and XZ carried out the experiments and analyzed the data. PH drafted
and revised the paper; QW designed and supervised the whole work.
All authors read and approved the final manuscript.
Acknowledgements
This work is supported by the National Natural Science Foundation of China
(No. 91122025, 21103127, 21101118), the State Major Research Plan (973) of
China (No. 2011CB932404), the Nano-Foundation of Shanghai in China (No.
11nm0501300), and the Shanghai Key Laboratory of Molecular Catalysis and
Innovative Materials (No.2012MCIMKF03).
Received: 30 November 2013 Accepted: 4 February 2014
Published: 15 February 2014
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doi:10.1186/1556-276X-9-76
Cite this article as: Hu et al.: A new nanosensor composed of laminated
samarium borate and immobilized laccase for phenol determination.
Nanoscale Research Letters 2014 9:76.
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