Sensors and Actuators B 240 (2017) 718725

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Sensors and Actuators B: Chemical

journal homepage: www.elsevier.com/locate/snb

Mesoporous hollow silica shells modied with functional diamine

groups show high-performance absorption capacity and selective
colorimetric response to copper ions in aqueous solutions
Ji Chen-hui a,1 , Li Jun-jie a,1 , Hou Chang-jun a,b, , Huo Dan-qun a , Yang Mei a , Zhang Liang c
a

Key Laboratory of Biorheology Science and Technology, Ministry of Education, College of Bioengineering, Chongqing University, Chongqing 400044, China
National Key Laboratory of Fundamental Science of Micro/Nano-Device and System Technology, Chongqing University, Chongqing 400044, China
c
National Engineering Research Center of Solid-State Brewing, Luzhou Laojiao Group Co. Ltd., Luzhou, Sichuan 646000, China
b

a r t i c l e

i n f o

Article history:
Received 10 May 2016
Received in revised form 5 September 2016
Accepted 6 September 2016
Available online 7 September 2016
Keywords:
Copper ions
Mesoporous hollow silica shells
Absorption materials
Colorimetric sensor
Cupron

a b s t r a c t
High-performance measurement and removal of copper ions is highly desirable in both clinical and environmental applications. Herein, an efcient, reliable and recyclable functional material was prepared
to adsorb and determine Cu2+ using N-[3-(trimethoxysilyl) propyl] ethylenediamine modied mesoporous hollow shells (HMS-NHs). By stepwise coating with mesoporous silica at highly mono-dispersed
PS spheres, removal of template materials, and modication with functional diamine groups, higher
absorption capacity of about 138.58 mg/g was obtained. After optimization of PS template size, thickness
of SiO2 layers, pore size of the shell, and etc, as-prepared HMS-NHs gave clear colorimetric response after
color development using cupron solution. Selectively measure Cu2+ in a wide concentration ranges from
0.025 to 49 M was observed with a detection limit around 0.025 M (3). More importantly, the functional absorbent can be regenerated by treatment with hydrochloric acid and maintains high efciency
upon repeated use for at least 10 times. Extensive investigation demonstrated that the HMS-NHs can
serve as not only high-performance absorption materials but also sensitive sensor for Cu2+ , thus offering
a good alternative for potential removal and detection of copper ions in real applications.
2016 Published by Elsevier B.V.

1. Introduction
As an important element in living organisms, copper ion plays an
essential role in a number of metalloproteins as cofactor to enable
physiological and pathological functions [13]. In low concentrations, Cu2+ is requisite to maintain normal functions of human
body. However, it would become highly toxic when used overdose,
leading to illness like chronic disease (such as diabetes, cardiovascular disease and atherosclerosis) [4,5], neurological disorders
(like Alzheimers disease) [69], and even cancer [10,11]. Studies also demonstrated that copper was required for oncogenic
mitogen-activated protein kinase signaling and tumorigenesis [12].
Given the versatile functions and toxicity associated with copper
metabolism, regulations have been set to restrict the amount of
Cu2+ in related foodstuff by ofcial organizations around the world.

Corresponding author at: Key Laboratory of Biorheology Science and Technology,

Ministry of Education, College of Bioengineering, Chongqing University, Chongqing
400044, China.
E-mail address: houcj@cqu.edu.cn (C.-j. Hou).
1
These authors contribute equally to the article.
http://dx.doi.org/10.1016/j.snb.2016.09.017
0925-4005/ 2016 Published by Elsevier B.V.

In drinking water, for instance, the World Health Organization

(WHO) has recommended 1.5 mg/L of Cu2+ as the maximum acceptable concentration while the maximum allowable level of Cu2+
ion has been set at about 20 M by U.S. Environmental Protection
Agency (EPA) [13,14].
Currently, measuring Cu2+ in biological and environmental can
be realized using various instrumental techniques, which include
stripping voltammetry [1518], atomic absorption spectrometry
[19,20], inductively coupled plasma mass spectrometry [21,22],
and so on [2325]. Although those methods have been demonstrated with good performance, they also involve in inescapable
drawbacks like high cost, sophisticated pretreatment, requirement of professional operation, and limited accessibility to in-led
analysis. Therefore, a simple, rapid and convenient method for
easy measurement of copper ions is of particular importance
[26,27]. As an attractive technology, colorimetric sensors have
been widely explored due to merits of easy fabrication, low-cost,
ease of operation, convenient data acquisition and portability for
in-eld detection of analytes including glucose [28], amino acids
[29,30], toxic gas [31,32] and heavy metals [33,34]. However, apart
from the analytical performance those sensors obtained, a pre-

C.-h. Ji et al. / Sensors and Actuators B 240 (2017) 718725

concentration procedure is usually needed since a majority of trace

metal ions are found in concentrations below the detection limit of
colorimetry and in company with numerous interfering counterparts [3537]. In view of those problems, hollow spherical particles
with mesoporous shells would serve as a promising candidate to
enable high pretreatment efciency due to merits like large void
space and specic surface area, which is favorable for absorption
and storage [38]. Meanwhile, study showed that chemical grafting of N-[3-(trimethoxysilyl) propyl]ethylene-diamine (TPED) at
the surface of SBA-15 could serve as good absorbent for removal
of Cu2+ ions with very good selectivity [39,40], and more importantly, absorbed amount of Cu2+ can be determined by colorimetric
detection using a variety of synthesis ionophore [41,42].
In the present study, we sought to use HMSs as a substrate
and integrate its absorption capability with the selective afnity
of N-[3-(trimethoxysilyl) propyl] ethylne-diamine (TPED) towards
copper ions. Mono-dispersed silica mesoporous hollow spheres
with high absorption capablity can be prepared by many preconformed strategies and easily functionalized using silylating
reagents. We anticipate that successively modied HMSs would
present higher selectivity to copper ion, and subsequent color
development by cupron would ensure better colorimetric measurement of this heavy metal ion in real applications.

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immersed into THF to remove the template PS, and HMSs were collected by alternate centrifugation/washing with deionized water
and ethanol.
TPED modication of HMSs was processed by adding 1 g HMSs
into TPED aqueous solution of given concentration (V%), and
allowed to react for 6 h at 50 C. The diamine-functionalized HMSs
(HMS-NHs) were nally collected by centrifugation/washing with
deionized water before dried overnight.
2.3. Absorption and detection of the Cu2+ ions
Typically, 5 mg of HMS-NHs were added into solutions of Cu2+
of given concentrations in given volumes. After absorption for a
time at desired temperature (see details in the following parts), the
HMS-NHs were separated by centrifugation and added with 200 L
cupron solution for color development. To obtain color information,
20 L of the HMS-NHs solution was dipped into a 96-well plate and
scanned with a scanner (Epson Perfection V10). The images were
stored in BMP format at 350 dpi and analyzed using the ImageJ
software (National Institutes of Health) to acquire the average R,
G, B value. All the samples were tested repeatedly for at least three
times using deionized water as blank control throughout the study.
2.4. Evaluation on the absorption capacity and reusability

2. Experimental section
2.1. Reagents and stock solutions
N-[3-(Trimethoxysilyl)propyl]ethylenediamine (TPED), cupron,
Pluronic P123 (P123), Tetraethyl orthosilicate (TEOS), ethanol,
NaOH, ammonium nitrate (NH4NO3), hexadecyltrimethylammonium bromide (CTAB), potassium persulfate (KPS), PVP (K30),
Cupron (Sodium diethyldithiocarbamate) and metal salts were purchased from Aladdin reagent company (Shanghai, China), and used
without further treatment. 99% Styrene from KeLong Chemical
Company (Chengdu, China) was puried briey by washing (three
times) with aqueous NaOH (5 wt%), and neutralized by extensive
wash using deionized water before dried with calcium chloride
anhydrous (CaCl2 ). The cupron solution (0.1%, wt%) was prepared
with deionized water at desired pH = 8.5 adjusted by 0.1 M NaOH.
Milli-Q puried water was used throughout the experiments.

5 mg of HMS-NHs were add into 11 mL Cu2+ solutions in a concentration of 10 mM and incubated for 30 min. The amount of
unabsorbed Cu2+ in the supernatant was measured by ICP-MS after
centrifugation. To evaluate the reusability, the Cu2+ -loaded HMSNHs were washed throughout with 0.1 M HCl and deionized water
alternately, and then dry at 60 C for 3 h before recycling use.
2.5. Real samples analysis
The water samples, including river water and spiked water, were
collected from Chialing River (Chongqing, China). These samples
were measured directly without further treatment. Accurate Cu2+
concentrations were determined by inductively coupled plasma
mass spectrometry (ICP-MS).
3. Result and discussion
3.1. Characterization of as-prepared HMS-NHs

2.2. Fabrication of diamine-functionalized HMSs

Using KPS as initiator, anionic polystyrene (PS) spheres were
prepared by emulsier-free emulsion polymerization (EFEP) following a procedure reported previously [43]. Typically, 6.5 mL of
Styrene and a predetermined amount of PVP were added into
50 mL deionized water under mild stirring for 20 min. Then, the
mixture was degassed with nitrogen gas for 10 min at room temperature before 0.15 g KPS in 10 mL deionized water was applied.
After reaction in water bath at 70 C for 24 h, resultant PS spheres
were harvested by centrifugation and desired diameters can be
controlled by adjusting the amount of PVP (wt% = 4.13%, 2.48%, or
0.41%).
To realize surface coating of SiO2 layer, 1 g of PS spheres were
added into a mixture containing 0.1 g CTAB (or P123), 13 g deionized water, 9 g ethanol and 0.5 mL ammonium hydroxide. After
sonication for 120 min, 0.4 g TEOS was added dropwise and the mixture was kept magnetically stirring for 48 h at room temperature.
The mesoporous SiO2 coated latex was collected by centrifugation
and washed alternately with deionized water before removal of
CTAB using NH4 NO3 solution (6 g/L, in ethanol). The procedure for
SiO2 coating was repeated for several times until desired number
of layers were obtained. As-prepared powder was subsequently

Fig. 1 displays the SEM images of PS spheres obtained at three

PVP concentrations, SEM and TEM images of resultant HMS, and
related size distributions. All the PS templates showed clear globose appearance in mono-dispersed size distributions. Since PS of
large sized were prepared from small particles using seed-growing
method, small PS were observed in the 1400-nm samples. The
diameters and the coefcient of variation of PS spheres decreased
with the increase of PVP concentration, as summarized in Table
S1. Concentration of PVP (wt%) at 4.13, 2.48 and 0.41 resulted in
PS particles of diameter of 198 6, 490 20, and 1341 214 nm,
respectively. The HMSs with different diameters were synthesized
using PS spheres of expected size as cores. After coating of SiO2 layer
at the surface and successive removal of template, mesoporous hollow silica shells were prepared. As is shown in the SEM images, the
HMSs showed a rough surface appearance composed with dumps in
nano-size, the morphology of which largely improved the surfaceto-volume ratio and is favorable for absorption enhancement. The
TEM images suggested that the particles is completely hollow in the
inner core, and the average outer shell thickness were measured to
be 37.5 nm, 32.8 nm, and 53.4 nm, respectively (Scheme 1).
HMSs were then decorated with TPED to obtain diaminefunctionalization for specic Cu2+ absorption. Fig. 2 (left) shows

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C.-h. Ji et al. / Sensors and Actuators B 240 (2017) 718725

Fig. 1. SEM and TEM images of as-prepared functional materials. From left to right each represents SEM image of PS spheres, SEM and TEM image of hollow mSiO2 , and
corresponding size distributions. From upper to down, 200, 500 and 1400 nm.

Scheme 1. Illustration of the procedure to fabricate the functional hollow mesoporous SiO2 (mSiO2 ) for copper ions absorption and detection.

Fig. 2. IR spectra and TGA curves of hollow mSiO2 (HMS), TPED modied HMS before (HMS-NH) and after (HMS-NH-Cu) absorption of copper ions.

C.-h. Ji et al. / Sensors and Actuators B 240 (2017) 718725

the IR spectra of HMS, TPED modied HMS before (HMS-NH) and

after (HMS-NH-Cu) absorption of copper ions. For all samples,
typical absorption peaks around 800 cm1 and 1080 cm1 were
observed, which are associated with the stretching vibrations of
Si O Si and Si O, respectively. Two apparent absorptions near
1640 cm1 and 3440 cm1 might be attributed to the OH vibration of physically adsorbed water. After TPED modication, the
HMS-NH sample showed absorption at 2920 cm1 and 700 cm1 ,
which also appeared in the spectra of HMS-NH-Cu. These two peaks
each link to aliphatic C H stretching vibration and N H deformation vibration resulted from the side chain of the silylating
agent. A clear absorption at 950 cm1 , sign of Si O and Si O C
stretching vibrations, in the HMSs shows signicant decrease in
HMS-NH and HMS-NH-Cu, which is possibly due to cleavage of the
silicon hydroxyl group (Si OH) and silicon ester ( SiOCH3) after
crosslinking reaction [39]. And, it is worth to note that, absorption
peak at 1480 cm1 (C N stretching vibration) at HMS-NH shift to
1460 cm1 HMS-NH-Cu due to association of Cu2+ with NH2 and
HN in the functional diamine groups, which is consistent with
the former study [39]. Measurement on the zeta potential of the
samples also suggested that HMSs exhibited negative charges due
to OH groups at the SiO2 surface (Fig. S1A), which turned positively charged after TPED modication due to presence of amino
groups (Fig. S1B). Absorption of copper ions did not exert signicant
inuence on the zeta potential of HMS-NH (see Fig. S1C). Further
thermogravimetric analysis (TGA) was applied to measure the relative contents of functional groups at the surface of HMS-NH and
absorption of Cu2+ on HMS-NH. Content of TPED on the surface of
HMS-NH was measured to be about 11.44%, while the saturated
absorption capacity was calculated to be around 150 mg/g, similar
to that measured with ICP-MS (138.58 mg/g). The absorption capacity is much higher than those reported in former studies [44,45]. In
contrast, HMS-NH of 500 nm and 1400 nm each showed an absorption volume of 45.15 and 30.69 mg/g, respectively (Table 1).
3.2. Optimization of the preparation procedure
To investigate the inuence of the diameters of template on
the absorption ability toward Cu2+ , three kinds of PS spheres with

721

Table 1
BET characterization of HMS, HMS-NH and HMS-NH after saturated Cu2+ absorption.
Sample

SBET (m2 /g)

Pore Volume (cc/g)

Pore Radius ()

HMS-200 nm
HMS-NH-200 nm
HMS-NH-Cu-200 nm
HMS-NH-500 nm
HMS-NH-Cu-500 nm
HMS-NH-1400 nm
HMS-NH-Cu-1400 nm

972.02
682.93
423.07
644.79
412.45
606.99
365.26

1.59
1.19
0.74
1.05
0.67
0.99
0.59

2.34
2.31
1.90
2.33
2.13
2.23
1.94

mean diameters (Dm) of 200, 500, and 1000 nm were synthesized

by adjusting the amount of PVP. Fig. 3 summarized the effects of
diameters of PS templates, number of SiO2 layers, surfactants for
pore formation, and also TPED concentrations on the responses of
resultant HMS-NHs towards Cu2+ at 1, 10 and 100 M (2 mL solution with static absorption for 1 h). In the presence of the same
copper ion amount, the HMS-NHs showed an increase of colorimetric response with decreasing diameter of templates in all three
concentrations, which could be explained by the increased specic
surface area when diameters of PS core decrease. Therefore, HMSs
obtained from PS in 200 nm were selected in following-up studies.
Then, the thickness of mesoporous silica shells and pore size were
studied since they determined the absorption capability and mass
transfer of Cu2+ upon absorption in the matrices.
As is observed in Fig. 3B, with growing numbers of SiO2 coating, colorimetric response (measured as B) rst increase and then
declined slowly. Although an increase in mesoporous SiO2 layer is
benecial for the improvement of absorption capacity, the thick
shell may restrict the transfer of Cu2+ in the SiO2 matrices, and
presents a physical barrier for further absorption. 4 cycles of coating
were thus chosen to maximize the colorimetric response. The surfactant used in the shell formation process determines the pore size
of HMS-NHs and is also an important for nal absorption capacity.
Comparison between P123 and CTAB in Fig. 3C demonstrated that
HMS-NHs prepared with CTAB is more preferable in view of colorimetric response, and more importantly, elimination of template
PS core led to clear improvement of response in all applied Cu2+
concentrations. The effect of the concentration of TPED was also

Fig. 3. inuence of size of PS template spheres (A), number of SiO2 layers (B), surfactants (C), and TPED concentrations (D) on the response of as-prepared functional HMS.

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C.-h. Ji et al. / Sensors and Actuators B 240 (2017) 718725

Fig. 4. Inuence of reaction time (A), temperature (B), and volume of sample (C) on the response of as-prepared functional HMS.

investigated so as to further improve the absorption capacity. As is

shown in Fig. 3D, the highest colorimetric response was obtained
at TPED concentration of 3.0%. It seems that lower TPED concentration (1.5%) is not sufcient to endow HMSs with enough diamine
group for maximum Cu2+ absorption, whereas excess TPED (4.5%)
might block up the pores of HMSs, thus impairing mass transfer
of Cu2+ into inner shell. Therefore, 3.0% TPED were applied in the
following investigation.
3.3. Optimization of the detection condition
According to our former study, an electromagnetic stirring
device was applied to stir the solution to enable dynamic absorption by the HMS-NHs. Fig. 4 shows the inuence of absorption time,
temperature and solution volume on the colorimetric response of
HMSs. With an increase of absorption time (Fig. 4A), the HMSs
demonstrated clear increase in B until it reached to the maximum
after 15 min, and no further improvement in response was observed
in prolonged time. It indicates that absorption of Cu2+ by HMSs
would reach an equilibrium in 15 min, which was thus considered as optimized reaction time. Temperature-dependent increase
of response in the range of 2070 C was shown in Fig. 4B. The
maximum B was achieved at 50 C and attened with increased
temperature from 50 to 70 C. It is expected that temperature
would exert signicant inuence on the absorption of HMS-NHs
by accelerating the motion of Cu2+ in solution. Generally, higher
temperature enhances the diffusion of Cu2+ ions and raises the
chance of effective collision between Cu2+ and the functional material [46], thus in turn, leads to improved adsorption of Cu2+ and
higher color response. The maximal interaction reached at 50 C,
and further increase of temperature did not make a difference for
the response. Therefore, we selected 50 C as favorable temperature. Since the colorimetric response of HMSs is determined by
the absolute amount of Cu2+ absorbed, we thus carried out further
investigation on the inuence of volume of Cu2+ solution (Fig. 4C).
It clearly suggested that colorimetric response intensied when
more Cu2+ solution applied from 3 to 11 mL, and increase of the volume from 11 to 15 mL did not result in signicant higher response.
Although using more Cu2+ solution would further improve the nal
absorption of Cu2+ in low concentration, in which the HMSs do not
reach a saturation, it is reasonable to choose the volume of 11 mL
as favorable volume for analysis of small amount samples.
3.4. Absorption and detection of Cu2+ by HMS-NHs
After optimization of the detection conditions, the ability of
HMS-NHs to absorb and detect copper ions was examined. Typically, 5 mg of HMS-NHs were put into ve different solutions of
11 mL with tenfold gradient concentrations (0, 0.1, 1.0, 10.0 and
100.0 M). After stirring for 15 min at 50 C, the HMS-NHs were
separated by centrifugation. In Cu2+ concentrations higher than

10.0 M, the nano-particles showed distinguishable color changes

without any chemicals added. When developing the nal color
using cupron, clear blue to yellow color was observed by nakedeyes in very low concentrations. Despite no evident color changes
were observed in lower concentrations for pure nano-particles, a
dark brown color would appear after addition of cupron, and, as
expected, the intensity is highly associated with the concentration of Cu2+ . As shown in Fig. 5, a decrease in the B value was
observed when decreasing the concentration in the solution. The
B value is linearly correlated with the concentration of Cu2+ in
the range from 0.025 to 1.0 M. The correlation coefcient is measured to be R2 = 0.9912, and the detection limit calculated as 3 is
about 0.025 M, which is much lower than the critical standard
level of Cu2+ allowed in drinking water (WHO standard, 30 M;
EPA and China standard, 20 M). In the presence of higher Cu2+
concentrations (higher than 1.0 M), the colorimetric response
is exponentially associated with the concentration. The highest
distinguishable concentration is around 49 M by direct measurement.
In practical applications, selectivity is as important as sensitivity in the measurement of a given analyte. Therefore, feasibility
of as-prepared HMS-NSs for selective determination of copper ion
was investigated in the presence of possible interfering counterparts following the optimized procedures. The interfering ions was
prepared at a concentration of 100 M and detected using the
HMS-NHs with 10.0 M of Cu2+ solution as control. The results are
displayed in Fig. 6. No change of B value over 10 after absorption
of interfering ions was observed while that of the control was as
high as about 180, despite that the concentration of the interference
is 10-times higher than the control Cu2+ solutions. These ndings
demonstrated that the HMS-NHs can serve as high efcient adsorption and detection material for Cu2+ ions with preferred sensitivity
and selectivity.

3.5. Evaluation on reusability of HMS-NHs and feasibility for real

application
The adsorption capacity of the Cu2+ -adsorbed HMS-NHs can be
regenerated by complete washing with HCl solutions and deionized
water. As shown in Fig. 7, the B value changes can re-obtained
with no signicant change upon repeated washing. After ten recycling use, similar absorption capacity was obtained. Those results
demonstrate that as-prepared HMS-NHs have high chemical stability and can be applied for repeated use, which is high benecial
in practical applications.
Lastly, further application to analyze real samples was testied
using water samples from Chialing River (Chongqing, China). Before
the recovery test, the accurate concentrations in the samples were
measured using ICP-MS. After spiked with 1.0 and 10.0 M Cu2+ , the
recovery obtained by the HMS-NHs were found to be 95.94% and
103.57%, respectively (see Table S2). In both cases, the relative error

C.-h. Ji et al. / Sensors and Actuators B 240 (2017) 718725

723

Fig. 5. Real images of as-prepared HMS-NHs absorbed Cu2+ of different concentrations after cupron derivation (in three batches), and linear tting of response (B) with
respect to Cu2+ concentrations.

Fig. 6. interference study of as-prepared functional HMS in the presence of possible interfering counterparts. Cu2+ is 10 M while other ions are 100 M.

Fig. 7. inuence of washing times on the recovery of response of as-prepared functional HMS, and tests on its reusability after 10 cycles.

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C.-h. Ji et al. / Sensors and Actuators B 240 (2017) 718725

was not higher than 5%, suggesting that the practical applicability
of the HMS-NHs for efcient adsorption and reliable measurement
of Cu2+ ions in environmental samples.
4. Conclusion
In this study, an efcient, reliable and recyclable functional
material of N-[3-(trimethoxysilyl) propyl] ethylenediamine modied mesoporous hollow shells was developed for adsorption and
determination of Cu2+ . Using highly mono-dispersed PS spheres as
template, stepwise coating with mesoporous silica, and removal of
core materials and nal modication of functional diamine groups,
higher absorption capacity for Cu2+ was realized with a maximum value of about 138.58 mg/g. After optimization of preparing
and also detection conditions, the diamine-functionalized HMSs
displayed an excellent performance to adsorb copper ion and
gave clear color response after addition of cupron solution. The
functional material can be directly used to measure wide Cu2+ concentrations between 0.025 and 49 M, with a low detection limit of
0.025 M. Therefore, as-prepared HMS-NHs would serve not only
high-performance absorption materials but also sensitive sensor
for copper ions. More importantly, it can also be regenerated by
treating with hydrochloric acid and maintain high efciency upon
repeated use for at least 10 times. The advantage of as-prepared
materials involves the high absorption capacity of Cu2+ and easy
quantication based on colorimetric measurement. Further functionalization like magnetic decoration is expected to enable easy
separation of the absorbent from samples into standard analysis
buffers [47]. Nevertheless, our study presents a more selective and
sensitive method to detect copper ion in aqueous solutions, and
demonstrates unlimited potential for adsorption and determination in real applications.
Acknowledgments
The authors would like to acknowledge the nancial support from Chongqing Graduate Student Research Innovation
Project (CYB14013), National Natural Science Foundation of
China (No. 31171684), Key Technologies R&D Program of China
(No. 2014BAD07B02), the Workstation in Sichuan Province (No.
GY2015-01), and Brew Microorganisms Technology and Application of Key Laboratory Project in Sichuan Province (No. NJ2014-03).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.snb.2016.09.017.
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Biography

Professor Changjun Hou completed his Ph.D. in biomedical engineering in 2004 at Chongqing University. After a
period of research at the University of Illinois at UrbanaChampaign as a visiting scholar, he returned to China and
got tenure at the college of bioengineering in Chongqing
University. In 2010, he became a full professor in biomedical engineering. His scientic interests rest on the design
and construction of biochemical sensing systems based on
porphyrins and other sensitive materials.