Electrochimica Acta 192 (2016) 158–166

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Reversible Switched Detection of Dihydroxybenzenes Using a

Temperature-sensitive Electrochemical Sensing Film
Yuanqing Zhoua,1, Chao Chena,1, Jia Zhaob , Junjie Feia,* , Yonglan Dinga , Yuanli Caia,c
a
Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan
411105, PR China
b
College of Resource and Environment, Hunan Agricultural University, Changsha 410128, PR China
c
Department of Polymer Science and Engineering, Soochow University, Suzhou 215123, PR China

A R T I C L E I N F O A B S T R A C T

Article history: A composite sensing film (PGS), consisting of poly(N-isopropylacrylamide)101-b-poly(2-acrylamidoethyl

Received 6 November 2015 benzoate)37 (PNIPAM101-b-PAAEB37), graphene oxides (GO) and short multi-walled carbon nanotubes
Received in revised form 21 January 2016 (SMWCNs), was fabricated and modified onto a working electrode. The sensing film served as a reversible
Accepted 25 January 2016
switch for electrochemical detection, with the switching behaviour responding to thermal stimuli. Cyclic
Available online 28 January 2016
voltammetry of hydroquinone (HQ) and catechol (CC) at the PGS film-modified electrode displayed large
peak currents when the temperature was above the lower critical solution temperature (LCST) of
Keywords:
PNIPAM101-b-PAAEB37. These large currents disappeared at low temperature. Interestingly, the composite
graphene oxide
multi-walled carbon nanotube
film showed reversed electrochemical “on/off” behaviour as compared to previously reported switchable
electrochemical sensor electrodes, which were modified only with temperature-responsive polymers. This behaviour can be
temperature-responsive polymer attributed to the temperature-dependent phase transition of PNIPAM101-b-PAAEB37 and cooperative
electrochemical “on/off” detection effects of the other two functional components (SMWCNs and GO). The repeatable “on/off” switching of
the voltammetric responses of HQ/CC on the PGS-modified electrode were achieved via regulating the
solution temperature. This research provides a new type of temperature-controlled switchable electrode
with potential applications in the design of novel sensors, fuel cells and electronics.
ã 2016 Elsevier Ltd. All rights reserved.

1. Introduction Stimuli-responsive polymers, which exhibit changes in confor-

Chemically modified electrodes with reversible “on/off” switch-
ing or tunable interfacial properties toward external physicochem-
ical signals are intriguing systems for fundamental research, and
offer great promise in such fields as switchable biosensors for
biomedical applications [1,2], switchable fuel cells [3], electro-
chemical information processing systems [4], and other electro-
chemical devices [5]. One approach to switchable electrode
construction involves applying metallic or magnetic species in
electrochemical devices. The electrode interfacial properties (e.g.,
conductivity) can be significantly tuned by variable potentials or an
external magnetic field [6–11]. For instance, Cu2+ ions in a poly
(acrylic acid)/CdS matrix immobilized on an Au electrode surface
were reduced to metallic clusters and then oxidized back to the
cationic state by altering the potentials, which caused dramatic
changes in the conductivity of the polymer layer [7].
* Corresponding author. Tel.: +86 731 58298876; fax: +86 731 58292251.
E-mail address: fei_junjie@xtu.edu.cn (J. Fei).
1
These author contributed equally to this work.
mation or structure due to external stimuli [12–17], provide
another approach to switchable electrode construction. Electrode
surfaces coated with responsive polymers can significantly change
their interfacial properties (e.g., charged state, permeability, and
pH [18–20]) in response to external signals such as light,
temperature or chemical/biochemical input, and show tunable
or switchable electrochemical behaviours [21–27]. Tam [19]
reported that indium tin oxide (ITO) electrodes modified with
poly(4-vinyl pyridine) (P4VP) brushes showed switchable interfa-
cial activity toward redox species. This was due to the high
permeability for redox species of the protonated, swollen P4VP
brush state (electrochemical “on” state) and the impermeability of
the deprotonated, hydrophobic, shrunken P4VP brush state
(electrochemical “off” state). Temperature-sensitive polymers
can undergo swelling–shrinking phase transitions in response to
thermal stimuli [28,29], and have attracted interest as tempera-
ture-controlled electrochemical switch devices [30,31]. Poly(N-
isopropylacrylamide) (PNIPAM) has been extensively studied as a
temperature-sensitive polymer in the sensor field. Its LCST is
approximately 32
C [32,33], just within the manageable temper-
ature range for conventional electrochemical experiments.

http://dx.doi.org/10.1016/j.electacta.2016.01.183
0013-4686/ ã 2016 Elsevier Ltd. All rights reserved.
 Y. Zhou et al. / Electrochimica Acta 192 (2016) 158–166
PNIPAM films fabricated on electrode surfaces show a reversible,
temperature-controlled “on-off” property toward redox probes.
Specifically, electrochemical responses of redox probes appeared
when the PNIPAM brush was in the swollen state (below 32
C) but
disappeared when the PNIPAM brush was in the shrunken state
(above 32
C) [24].
Carbon nanomaterials such as fullerenes, carbon nanotubes,
and graphene exhibit unique optical, electronic, and catalytic
properties. In the sensor field, carbon nanomaterials used in
electrode modification can accelerate signal transduction through
catalytic activity, conductivity, and biocompatibility [34–37].
Graphene oxide (GO), a carbon nanomaterial, possesses a two-
dimensional, graphene-like structure with oxygen-containing
functional groups such as epoxide,  OH, and COOH. Due to
this structure, GO exhibits good hydrophobicity, moderate
conductivity, high chemical stability and excellent electrochemical
properties, and can act as a support for the deposition of inorganic
nanocatalysts or polymers. GO is widely used in the sensing field to
facilitate or mediate the charge/electron transfer between the
electroactive species and the electrode surface [38,39]. The
integration of stimuli-responsive polymers and carbon nano-
materials generates hybrid systems that combine the properties of
the nanomaterials with stimuli-responsive functions, to obtain
switchable or tunable electronic, photonic and catalytic properties
[40–45]. To date, hybrid materials have attracted substantial
attention and have extensive applications in the sensor field
[46,47]. A major goal of such studies is linked to achieving
synergistic efforts to bring advanced properties to the hybrid
materials, which can improve upon their individual properties
[48].
In this paper, a hybrid material consisting of the temperature-
sensitive copolymer PNIPAM101-b-PAAEB37, GO and SMWCNs was
utilized to develop a temperature-controlled switch electrode.
PNIPAM101-b-PAAEB37 contains benzene rings, which can be
noncovalently attached to GO surfaces through p–p stacking
interactions, which can improve the stability of the hybrid film [49].
The electrochemical responses of hydroquinone (HQ)/catechol (CC)
Scheme 1. Reversible, temperature-controlled “on/off” electrochemical response of HQ/CC at the PGS interface.
159
at the PGS-modified electrode were switched off when PNIPAM101-
b-PAAEB37 was swollen, but switched on while PNIPAM101-b-
PAAEB37 was shrunken (shown in Scheme 1). This switchable
behaviour was reversed from that of previously reported switchable
electrodes (modified only by stimuli-responsive polymers), which
were switched off in their hydrophobic shrunken state and
switched on in their swollen state [19,24]. The opposite “on/off”
behaviour of the composite PGS electrode can be attributed to the
cooperative, synergistic effect of PNIPAM101-b-PAAEB37, GO and
SMWCNs in response to temperature stimuli. The PGS electrode also
showed reversible and repeatable electrochemical “on-off” proper-
ties through controlling the solution temperature.
2. Experimental section
2.1. Reagents and Materials
SMWCNs (OD <8 nm, Length: 0.5–2 mm, Purity >95 wt%) were
obtained from the Chinese Academy of Sciences, Chengdu Organic
Chemistry Company. Hydroquinone (HQ) and catechol (CC) were
purchased from Shunyi Chemical Company of China and used
without further purification. GO was prepared according to
previous procedures [50]. PNIPAM101-b-PAAEB37 was prepared
according to previous procedures [51]. Synthesis details of
PNIPAM101-b-PAAEB37 and its 1H NMR and GPC data are presented
in the Supplementary Material, Fig. S1 and Fig. S2. All other
chemical reagents were of analytical grade. Water was purified
twice by distillation.
2.2. Fabrication of the Modified Electrodes
Glassy carbon electrodes (GCE) were carefully polished with
0.5-mm alumina on a polish cloth, followed by sequential cleaning
for 5 min with ethanol and double-distilled water in an ultrasonic
bath, then dried in air before use.
The GO solution (45 mL, 2 mg mL1) was added to a PNIPAM101-b-
PAAEB37 aqueous solution (75 mL,10 mg mL1), and the mixture was
160 Y. Zhou et al. / Electrochimica Acta 192 (2016) 158–166

sonicated for 10 min in an ice-water bath to yield a suspension
solution of PNIPAM101-b-PAAEB37/GO (PG). The resulting dispersion
solution was stable at 5
C in the refrigerator for months with no
precipitation. SMWCNs (0.6 mg) were added to PNIPAM101-b-
PAAEB37 solution (1 mL, 10 mg mL1), and this mixture required
shaking immediately preceding further use. The PNIPAM101-b-
PAAEB37/GO/SMWCNs (PGS) solution was formed by mixing the
PNIPAM101-b-PAAEB37/SMWCNs (PS) solution with the PG solution
at a 1:1 (v/v) ratio. Then, 6 mL of the PGS solution was placed onto the
surface of a clean GCE and dried at room temperature to form a
polymer composite film on the GCE. The PG electrode was obtained
by dropping 6 mL of the PG solution on the surface of a GCE.
Similarly, the GS electrode was obtained by dropping the mixed
solution of GO and SMWCNs on a GCE.
2.3. Electrochemical measurements
Electrochemical experiments were performed at a CHI
630 electrochemical workstation using a conventional three-
electrode cell. One of the modified electrodes was used as the

Fig. 1. SEM images of (a) GO, (b) SMWCNs, (c) PG composite film, (d) PS composite film, and the (e) PGS composite film. Inset of (b): 40000 image of SMWCNs.
 Y. Zhou et al. / Electrochimica Acta 192 (2016) 158–166 161

working electrode, a platinum wire was employed as the counter

electrode and a saturated calomel electrode served as the reference
electrode. During the electrochemical measurements, all electro-
lyte solutions were purged with high-purity nitrogen for at least
20 min and were then maintained under nitrogen atmosphere. A
Zahner Zennium electrochemical workstation (ZAHNER-ELEKTRIK
GmbH & Co. KG) was employed for electrochemical impedance
spectra (EIS) measurements. A phosphate buffer solution was used
as the supporting electrolyte. The surface morphology of different
composite films was observed by using a JSM-6610Lv scanning
electron microscopy system (SEM, JEOL, Japan) at an accelerating
voltage of 30 V. Prior to SEM analysis, samples were coated with a
gold layer.

3. Results and Discussion

3.1. SEM Characterization

The surface morphologies of GO, SMWCNs, PG, PS, and PGS

films are depicted in Fig. 1. GO shows a lamellar shape with a folded
structure and resembles a piece of folded paper (Fig. 1a). The
SMWCNs display an expected uniform nanofiber structure.
Because the SMWCNs were not functionalized, some agglomera-
tion appeared, and the dispersion of the SMWCNs in the
PNIPAM101-b-PAAEB37 matrix became inhomogeneous, as the
arrows show in Fig. 1d. PG is a homogeneous composite film
(Fig. 1c), indicating that GO sheets are homogeneously imbedded
into the polymer matrix, and confirming the good compatibility
and strong interfacial adhesion between GO and the PNIPAM101-b-
PAAEB37 matrix. Unlike the surface morphologies of PG and PS, PGS
appears to be piled up in thick cakes (Fig. 1e), clearly indicating the
presence of SMWCNs aggregates in this film, which increases the Fig. 2. A. Electrochemical impedance spectra obtained at different modified
film thickness. electrodes in supporting electrolyte (20
C). a(!) PGS/GCE; b(*) PNIPAM101-b-
PAAEB37/GCE; c(^) PG/GCE; d(~) GO/GCE. B. Electrochemical impedance spectra
obtained at the PGS/GCE upon stepwise heating of the supporting electrolyte from
3.2. EIS study of Different Electrodes and EIS Temperature Effect of the 26 to 40
C. Frequency range: 0.1 Hz to 100 KHz; Supporting electrolyte: 0.1 mol L1
KCl containing 5 mmol L1 K3[Fe(CN)6]/K4[Fe(CN)6] (1:1).
PGS Electrode

EIS is often used as a tool to investigate electron transfer

blocking effects on electrode surfaces in various sensors or
interfacial electron transfer rate. The result also shows that
biosensors, and the switchable/tunable operation of electrochem-
SMWCNs are successfully embedded in the composite film.
ical gates based on polymer films [52]. The semicircle diameter in
The temperature-dependent EIS spectra of PGS electrodes were
the complex EIS plane plot of Z“ against Z‘ reflects the electron
also studied in the presence of redox probes [Fe(CN)6]3/4
transfer resistance (Rct). Based on the Rct of different modified
(Fig. 2B). Upon stepwise heating of the solution from 26
C to 30
C,
electrodes, we can obtain their interfacial impedance change,
the semicircle diameters of the EIS decreased slightly, but a sharp
which is related to interfacial properties such as permeability and
decrease in the semicircle diameters was observed upon heating to
conductivity. Fig. 2A shows the EIS results of different modified
32
C. The semicircle diameters remain smaller, with little change,
electrodes toward soluble redox probes [Fe(CN)6]3/4. The Rct at
upon continued heating, indicating a low interfacial electron
PNIPAM101-b-PAAEB37/GCE (Fig. 2A curve b) is smaller than that
transfer resistance of PGS/GCE above 32
C and a large electron
obtained at PG/GCE (Fig. 2A curve c), reflecting fast electron
transfer resistance below 32
C. The EIS spectra also show that
transfer kinetics at the first electrode. Because PNIPAM101-b-
modified electrodes without PNIPAM101-b-PAAEB37 presented no
PAAEB37 is swollen at the 20
C testing temperature, diffusional
temperature-responsive behaviour from 26
C to 36
C. The
redox probes [Fe(CN)6]3/4 can permeate from the swollen
changes of the Rct values in the PGS film above and below 32
C
polymer film to the electrode surface [19,24], resulting in enhanced
may therefore be attributed to the temperature-responsive phase
electron transfer kinetics at PNIPAM101-b-PAAEB37/GCE. The PG
transition behaviour of PNIPAM101-b-PAAEB37 at 32
C (Fig. S3).
composite film consisting of GO and PNIPAM101-b-PAAEB37
Upon stepwise heating above 32
C, PNIPAM101-b-PAAEB37 under-
displays the largest Rct effect (Fig. 2A curve c) among the four
goes hydrophobic shrinkage, allowing the SMWCNs embedded in
modified electrodes, although the GO film exhibits the fastest
the film to act as conductive channels, resulting in a decreased Rct.
interfacial electron transfer (Fig. 2A curve d). The large Rct effect of
Below 32
C, PNIPAM101-b-PAAEB37 is in a swollen state, leading to
PG/GCE may be attributed to the poor permeability of GO toward
a widened distance among GO sheets that cuts off conductive
redox probes because of its two-dimensional planar structure and
channels, causing a higher Rct. This EIS result shows that a PGS-
the poor conductivity of PNIPAM101-b-PAAEB37. When SMWCNs
modified electrode can act as a temperature-controlled interfacial
are embedded in a PG film, the Rct decreases dramatically (Fig. 2A,
resistance switch, and it would be beneficial to study the
curve a). SMWCNs possess high electrical conductivity, so the
switchable electrocatalytic performance of the PGS composite
presence of SMWCNs in the composite film enhances the
toward redox species such as HQ/CC.
162 Y. Zhou et al. / Electrochimica Acta 192 (2016) 158–166

2.0

A 2.0 1.5

Current/1e-6A
c
1.0
0.5 b
a
1.5 0.0
Current / 1e-4A

-0.5

-1.0

1.0 -1.5
e
0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8
E/ V

0.5 d
a b c
0.0

-0.5

-1.0

0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8

E/ V
Fig. 4. Cyclic voltammograms of HQ at the PGS electrode in 0.1 mol L1 PBS solution

B 2.0 over a pH range of 5.0  8.5. Scan rate: 75 mV s1. Testing temperature: 37
C. Inset is
2.0 1.5 the plot of oxidative peak potential (^), reductive peak potential (&), and midpoint
potential (~) against pH in the pH range of 5.0  8.5.
Current/1e-6A

1.0 g
0.5 f
1.5
Current / 1e-4A

a
0.0

-0.5 When increasing scan rates from 10 to 220 mV s1, both the
1.0 -1.0
h reduction and oxidation peak currents increase linearly with the
0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8
E/ V increasing square root of the scan rates (v1/2) (inset of Fig. S5),
0.5 d demonstrating the typical diffusion-controlled process of HQ at the
PGS electrode.
0.0 f g a The influence of electrolyte pH on HQ peak potentials at the PGS
electrode was also studied. Fig. 4 shows that an increase of solution
-0.5 pH from 5 to 8.5 causes a negative shift in both the reduction and
0 0
oxidation peak potentials. Plots of Epa,Epc and E0 (E0 = (Epa + Epc)/2)
0

-1.0 as a function of solution pH are shown in the inset of Fig. 4. The E0

points from pH 5 to pH 8.5 result in a best-fit straight line with a
slope of 0.076 and an intercept of 0.56 (R = 0.9916). The
0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 experimental result of 76 mV pH1 is consistent with a 2H+-2e
E/ V transfer in the electrochemical reaction of HQ. However, the DEp
values of HQ at the PGS electrode vary with the pH of the
Fig. 3. A. Cyclic voltammograms of (a) bare GCE, (b) bare GCE + 2.7  105 mol L1
HQ, (c) PG/GCE + 2.7  105 mol L1 HQ, (d) PGS/GCE, and (e) PGS/GCE + 2.7  105
electrolyte solution. From pH 6.5 to 7.5, the DEp values are low with
mol L1 HQ. B. Cyclic voltammograms of (a) bare GCE, (f) bare GCE + 2.7  105 a pair of symmetric redox peaks, indicating a dramatic increase in
mol L1 CC, (g) PG/GCE + 2.7  105 mol L1 CC, (d) PGS/GCE, and (h) PGS/GCE + 2.7 the electron transfer rate and good reversibility of the HQ
 105 mol L1 CC. Solution temperature: 37
C. Scan rate: 75 mV s1. electrochemical reaction. However, DEp values increase with
increasing acidity or alkalinity of the electrolyte solution along
3.3. Electrochemical Behaviours of HQ and CC at the PGS Electrode with increased asymmetry in the CV peaks, indicating a slower
electron transfer rate and a more irreversible electrochemical
The cyclic voltammetry curves (CV) of HQ and CC at the bare, reaction of HQ at the PGS electrode. The influence of pH on CC peak
PG/GCE and PGS/GCE electrodes are presented in Fig. 3. A pair of potentials is similar to the results for HQ under the same test
redox peaks for both HQ and CC is observed at the three electrodes. conditions. The optimal pH range for detecting HQ/CC at the PGS
However, for the PG and bare electrodes, the CV responses are electrode thus appears to be from 6.5 to 7.5.
severely suppressed with remarkably decreased peak currents and The asymmetric voltammograms in acidic and alkaline PBS
increased DEp (DEp = Epa  Epc) (Fig. 3, curves b, c, f and g), solution can be described by the apparent charge transfer
indicating sluggish electron transfer kinetics. The CV response coefficient b. The kinetics of a redox couple described by the
current at the PGS electrode has a narrow DEp (Fig. 3, curves e and following equations is related to b [53]:
h) and is much larger than those at the bare GCE and PG electrodes,
kox = k0exp[bnf(E-E0 )]
0

demonstrating that the presence of SMWCNs in the composite film

enhances the electrochemical response and facilitates electron
transfer between HQ/CC and the PGS electrode, consistent with the
kred = k0exp[-anf(E-E0 )]
0

EIS results. The oxidation/reduction peaks at the PGS electrode

appear at +79/–35 mV for HQ (Fig. 3A, curve e) and +189/ + 75 mV where kox and kred are the rate constants for the oxidation and
for CC (Fig. 3B, curve h). The HQ and CC peaks are well-separated, reduction reactions at potential E, respectively. k
is the standard
indicating simultaneous detection of CC and HQ isomers in their rate constant, b is the apparent charge transfer coefficient, a = 1-b,
mixed solution using the PGS electrode (detailed results are n is the number of electrons transferred in the redox reaction, and
0
presented in Supplementary Material, Fig. S4). The CV responses of E0 is the formal potential of the redox couple. Because of the
HQ at different scan rates (10  220 mV s1) at the PGS electrode exponential form of b in these equations, minor changes in the
are shown in Fig. S5. A pair of redox peaks is obtained in each cycle. transfer coefficient should result in a dramatic change in the
 Y. Zhou et al. / Electrochimica Acta 192 (2016) 158–166
relative oxidation and reduction rates, and these changes may
affect the voltammetric peak shape. Changes in the transfer
coefficient are often associated with different mechanistic steps in
the electron transfer process. Fig. 4 displays the voltammetric
symmetry differences of acidic, neutral and alkaline PBS solutions,
suggesting different b values and different electrochemical
mechanistic steps for HQ at the PGS electrode. This result is also
consistent with the ‘scheme of squares’ model proposed by Jacq
[54]. This model was used to interpret the properties of quinone/
hydroquinone redox systems, and indicated that the electrochem-
ical reaction pathway depends heavily on the pKa values of the
species within the model, as well as the pH of the local
environment.
3.4. Temperature Effects on HQ/CC Electrochemical Behaviours at the
PGS Electrode
The electrochemical responses of HQ at the PGS electrode at
varied temperatures are shown in Fig. 5. No obvious peak currents
are observed when the temperature of the HQ solution is below
30
C, whereas a pair of peaks located at about +79/–35 mV is
obtained above 32
C. This pair of peaks belongs to the HQ
electrochemical response. This result demonstrates that the HQ
electrochemical reaction is switched on above 32
C and switched
off below 32
C (Fig. 5A), indicating that temperature can be used to
Fig. 5. A. Temperature-dependent cyclic voltammograms of HQ at the PGS
electrode in 0.1 mol L1 PBS solution (pH 7.0) from 24 to 40
C. B. The oxidation
and reduction peak current of HQ at the PGS electrode at different temperatures.
Scan rate: 75 mV s1; Concentration of HQ: 2.7  105 mol L1.
163
control the switching electrochemical reaction of HQ at the PGS
electrode.
When PNIPAM101-b-PAAEB37 was removed from the film, the
results show that there is no obvious difference in CV peak currents
from 24 to 40
C for the GS electrode (shown in Fig. S6), indicating
that the temperature-controlled electrochemical “on-off” switch-
ing behaviour of HQ at the PGS electrode may be attributed to the
temperature-responsive phase transition behaviour of PNIPAM101-
b-PAAEB37 at 32
C. The different phase states of PNIPAM101-b-
PAAEB37 in the PGS film above and below 32
C cause the film to
display differential electrochemical catalytic activity toward HQ.
Tam [19] and Song [24] reported that the “on-off” switching
electrochemical property at electrode surfaces modified by
stimuli-responsive polymers was related to the variable perme-
ability of the modified surfaces for diffusional redox probes. The
penetrative difference was caused by “swelling-shrinking” phase
transitions of stimuli-responsive polymers toward external stim-
uli. A polymer brush in the swollen state was permeable to the
redox probe, so the electrochemical response appeared, whereas in
the shrunken state, the dense polymer brush blocked transport of
the probes to the electrode surface, and the electrochemical
response was inhibited. In our study, the temperature-based “on-
off” switching behaviour of PGS surfaces is reversed from the above
result, and we are thus calling it an inverse electrochemical
temperature-switch. In the shrunken state of PNIPAM101-b-
PAAEB37 above 32
C, HQ displays a pair of well-defined redox
peaks (shown in Fig. 5A), indicating that the PGS electrode is active
toward HQ; in the swollen state below 32
C, the CV responses of
HQ are significantly suppressed, and the PGS electrode is inactive
(shown in Scheme 1). This opposite “on-off” switching behaviour
may be attributed to two key factors of the electrochemical activity
of the modified electrode toward redox species. One is interfacial
permeability, and the other is interfacial electron transfer rate. PGS
films possess poor permeability toward HQ because of the two-
dimensional planar structure of GO, which hinders HQ from
permeating to the GCE surface regardless of the swollen or
shrunken state of the PNIPAM101-b-PAAEB37 film. Therefore, the
electrochemical “on-off” switching activity of the PGS film is likely
related to its interfacial electron transfer rate. At T < 32
C, long
chains of PNIPAM101-b-PAAEB37 in the swollen state result in a
widened distance between GO sheets, introducing a large
interfacial electron transfer resistance, as measured by EIS
Fig. 6. Differential pulse voltammetry (DPV) of HQ and CC at the PGS-modified
electrode in 0.1 mol L1 PBS (pH 7.0) at temperatures from 24 to 40
C.
164 Y. Zhou et al. / Electrochimica Acta 192 (2016) 158–166
(Fig. 2B). Thus, the electrochemical responses of HQ are sup-
pressed. At T > 32
C, when PNIPAM101-b-PAAEB37 is in the
shrunken state, the distance between GO sheets shortens such
that SMWCNs embedded in the composite film can act as
conductive channels. This increases the electron transfer rate,
and the electrochemical responses of HQ are switched on. The
inverse electrochemical “on-off” switching behaviour of the PGS
film is thus attributed to the synergistic responses of PNIPAM101-b-
PAAEB37, GO and SMWCNs to temperature. When the HQ solution
temperature is raised from 24 to 30
C and from 32 to 40
C, the
peak currents show a small increasing trend (Fig. 5B), which may
be related to the increased diffusion behaviours of HQ or minor
adjustments of the PNIPAM101-b-PAAEB37 conformation upon
temperature changes in these ranges.
Fig. 6 shows differential pulse voltammograms of HQ and CC at
the PGS electrode at temperatures from 24 to 40
C. Highly
resolved and sensitive current responses of both HQ and CC are
obtained by differential pulse voltammetry (DPV) at the PGS
electrodes above 32
C, implying potential for simultaneous
detection of these compounds above 32
C by DPV. The current
responses of HQ and CC decrease sharply below 32
C and
Fig. 7. A. Reproducibly switching “on–off” CV response of HQ at the PGS electrode
between 26
C and 36
C, Concentration of HQ: 2.7  105 mol L1. Scan rate:
75 mV s1. B. Dependence of CV Ipa on solution temperature switched between 26
C
and 36
C.
Fig. 8. Reproducibly switching “on–off” DPV responses of HQ/CC at the PGS
electrode between 26
C and 36
C for eight cycles. Concentrations of HQ and CC:
2.7  105 mol L1.
disappear completely at 24
C, similar to CV responses of HQ at
varied temperature. Therefore, the temperature of the HQ and CC
solution can also be used to control the electrochemical “on-off”
switching reaction of HQ and CC at the PGS electrode. The reasons
for the electrochemical “on-off” reaction of HQ and CC are the same
as discussed above.
3.5. Electrochemical “On-Off” Behaviours at the PGS Electrode
Because the temperature-related phase transition process of
the PNIPAM chain is completely reversible [32], we studied the
reversibility of the temperature-related HQ electrochemical “on-
off” behaviours at the PGS electrode. Two typical temperatures,
26
C and 36
C, were selected to explore this behaviour (Fig. 7A). At
36
C, HQ displays a reversible CV peak pair with relatively large
peak current, indicating that the PGS film is in an “on” state; at
26
C, the CV response is significantly reduced and can hardly be
observed, and the film is in an “off” state. Reproducibly switching
“on-off” CV responses of HQ were achieved through repeated
heating and cooling of the PBS solution between 36
C and 26
C for
eight cycles, with no substantial degradation of the peak current
observed (Fig. 7B). When HQ and CC coexist in 0.1 mol L1 PBS (pH
7.0), the reversible and repeatable switching detection of HQ and
CC at the PGS electrode can be achieved via cyclic changes of the
solution temperature between 36
C and 26
C (Fig. 8). The
electrochemical reactions of HQ and CC at the PGS electrode are
very sensitive to the environmental temperature and present
reversible “on-off” behaviours. The reversible transition of the
electrochemical “on-off” switching activities of the PGS film
demonstrates the possibility of modulating the electro-catalytic
activity by temperature. This finding can potentially be applied in
switchable sensors and switchable fuel cells.
4. Conclusions
Electrode surfaces modified by a temperature-responsive
polymer composite sensing film consisting of PNIPAM101-b-
PAAEB37, GO and SMWCNs displayed a reversible and switchable
interface property toward temperature change. CV and DPV study
of HQ and CC at the PGS electrode indicated that reversible peak
pairs were observed above 32
C, where the PGS composite film
presented an electrochemical “switching on” state toward HQ and
 Y. Zhou et al. / Electrochimica Acta 192 (2016) 158–166
CC. Because no obvious peaks appeared below 32
C, the film
displayed a “switching off” state. The switchable property can be
attributed to the synergistic effects of all functional components of
the PGS film.
Acknowledgments
This research was financially supported by the NSF of China
(Grants No. 21475114 and 21275123), the Program for Changjiang
Scholars and Innovative Research Team in University (1337304),
Project of Hunan provincial natural science Foundation of China
(14JJ1019), and the Research fund for the doctoral program of
higher education of china, Ministry of education of China
(20134301110005).
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.
electacta.2016.01.183.
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