Switching the BZ Reaction with a Strong-Acid-Free Gel

Yusuke Hara,*
,
Yoshinori Yamaguchi,

and Hiroyuki Mayama

Nanosystem Research Institute (NRI), National Institute of Advanced Industrial Science and Technology (AIST), Central 5-2, 1-1-1
Higashi, Tsukuba 305-8565, Japan

Photonics Advanced Research Center, Osaka University, 2-1 Yamada-oka, Suita City, Osaka 565-0871, Japan

Department of Chemistry, Asahikawa Medical University, 2-1-1-1 Midorigaoka-Higashi, Asahikawa 078-8510, Japan
*S Supporting Information
ABSTRACT: In the present study, a novel gel with a semi-interpenetrating polymer
network (semi-IPN) that undergo the BelousovZhabotinsky (BZ) reaction without
the addition of a strong acid (HNO
3
or H
2
SO
4
) was developed. The required
concentrations of the BZ substrates, sodium bromate (NaBrO
3
) and malonic acid
(MA), under these conditions were higher than under the normal BZ reaction
conditions, involving the addition of a strong acid. The period of the BZ reaction with
the novel gel (semi-IPN BZ gel) decreased with increasing concentrations of NaBrO
3
and MA. Moreover, the connection of the semi-IPN BZ gel to a conventional BZ gel
facilitated the reaction in the latter through the propagation of the intermediates from
the former to the latter. The BZ reaction stopped when the conventional BZ gel was
disconnected from the semi-IPN BZ gel. These results demonstrate that the BZ
reaction in the conventional BZ gel underwent ono switching, controlled by its
attachment to the semi-IPN BZ gel. This ono switching mechanism would be
valuable in controlling actuators and robots without strong acids.

INTRODUCTION
Following the volume phase transition theory of polymers,
several researchers have tried to construct soft actuators using
gels.
18
These actuators can operate without gears, drive shafts,
and motors because they use external stimuli, such as
temperature, light, pH, ionic strength, and electric eld,
913
to directly convert mechanical energy into motion. The volume
phase transitions of gels are caused by Coulombic, hydrogen-
bonding, hydrophobic, and van der Waals interactions. To drive
gel actuators, external control devices are required to direct the
external stimuli to the stimulus-responsive polymer gels. In
contrast, a living organism moves autonomously by directly
converting chemical energy into mechanical energy in the body.
Therefore, the synthesis of polymer gels exhibiting autonomous
motion is essential for the development of unique chemical
actuators and robots. To achieve this goal, we focused on the
BelousovZhabotinsky (BZ) reaction. The BZ reaction has
been extensively studied because it is treated as a simple model
of a spatiotemporal structure such as a spiral pattern in an
unstirred solution and displays periodicity or multistability in a
stirred solution.
1424
The BZ reaction involves the oxidation of
an organic substrate by an oxidizing agent in the presence of a
metal catalyst under strongly acidic conditions. The metal
catalyst simultaneously undergoes spontaneous redox oscil-
lation and a periodic change in solubility. Self-oscillating gels
have been successfully developed by synchronizing the change
in solubility of the metal catalyst moiety due to the BZ
reaction.
2527
A self-oscillating polymer gel (initial BZ gel) is
composed of poly(N-isopropylacrylamide) [poly(NIPAAm)]
covalently bonded to the BZ catalyst Ru(bpy)
3
[ruthenium (4-
vinyl-4-methyl-2,2-bipyridine) bis(2,2-bipyridine) bis-
(hexauorophosphate)]. The poly[NIPAAm-co-Ru(bpy)
3
] gel
undergoes spontaneous swellingdeswelling, induced by the
BZ reaction under constant-temperature conditions. This gel,
having a cross-linked structure, transforms chemical energy
(energy derived from the BZ reaction) into mechanical work.
The construction of a soft actuator employing a generative
force and displacement of the self-oscillating gel was reported.
28
The energy conversion eciency of the self-oscillating polymer
gel was found to be higher than that of the conventional
stimulus-responsive-type gels owing to the absence of any
external control devices in the former. The displacement of the
poly[NIPAAm-co-Ru(bpy)
3
] gel was not adequate for their
application in chemical robots and actuators, necessitating
modications to enhance the displacement. The introduction of
a small amount of acrylamide-2-methylpropane sulfonic acid
(AMPS) into the poly[NIPAAm-co-Ru(bpy)
3
] gel increased the
displacement induced by spontaneous swellingdeswel-
ling.
2931
The rst chemical robots and actuators were
successfully constructed by exploiting the large displacement
of the gel containing AMPS (conventional BZ gel); these
included a self-walking gel and a matter-transporting gel.
30,31
The highly acidic environment required to drive the BZ
reaction poses a problem in the commercial application of self-
Received: November 6, 2013
Revised: December 13, 2013
Published: December 19, 2013
Article
pubs.acs.org/JPCB
2013 American Chemical Society 634 dx.doi.org/10.1021/jp410915p | J. Phys. Chem. B 2014, 118, 634638
oscillating gels in chemical actuators and robots because of
safety issues. Therefore, higher-pH conditions are necessary to
ensure safety. However, it is challenging to induce the BZ
reaction in the gels without strong acids (HNO
3
and H
2
SO
4
).
To initiate the BZ reaction in a gel without strong acids, we
fabricated a system in which the strong acid is incorporated into
the polymer gel.
To make the chemical environment suitable for driving the
BZ reaction, it is necessary to construct a gel system that
provides a high concentration of H
+
inside the gel but a lower
concentration outside the gel; the proton gradient originates
because of Donnan equilibrium. These conditions are similar to
those in the stomach of a living body. Therefore, we
synthesized a novel BZ gel with a semi-interpenetrating
network (semi-IPN) structure that facilitates a selective
decrease of pH inside the gel. One component of the novel
BZ gel (semi-IPN BZ gel) contained AMPS [poly(AMPS)],
resulting in a decrease in the pH of the gel. Network
components consisting of AMPS and a cross-linker were
employed to maintain the pH in the gel lower than the external
pH. The second component was a linear polymer chain
containing the Ru-catalyst moiety and a high concentration of
AMPS {poly[NIPAAm-co-Ru(bpy)
3
-co-AMPS]}. Poly-
[NIPAAm-co-Ru(bpy)
3
-co-AMPS] was selected as the second
network in the semi-IPN BZ gel because it oscillates at low
concentrations of H
+
owing to the high content of AMPS.
3234
Moreover, we rst detected that the BZ reaction without strong
acids was initiated when the conventional BZ gel was
connected to the semi-IPN BZ gel. On disconnecting the two
gels, the reaction was stopped only in the conventional BZ gel.
This is the rst demonstration of the ono switching of the
BZ reaction without the direct addition of strong acids,
regulated by the connection between the two gels. This ono
switching mechanism would be valuable in controlling actuators
and robots under mild pH conditions.

EXPERIMENTAL SECTION
Synthesis of the Second Network in the Semi-IPN BZ
Gel. The second network was synthesized using NIPAAm,
AMPS, Ru(bpy)
3
monomer, and 2,2-azobisisobutyronitrile
(AIBN). Poly[NIPAAm-co-Ru(bpy)
3
-co-AMPS) was synthe-
sized by radical polymerization in a mixture of ethanol and
water (1:1 wt/wt) at a total monomer concentration of 20 wt %
at 60 C. The feed composition (wt %) was NIPAAm/
Ru(bpy)
3
/AMPS = 40:10:50. The resulting reaction mixture
was dialyzed against ethanol for 4 days and then water for 3
days and subsequently freeze-dried.
Synthesis of the Semi-IPN BZ Gel. AMPS (0.5 g),
(NH
4
)
2
S
2
O
8
(16.5 mg) as an initiator, and poly(ethylene
glycol) dimethacrylate (93.1 mg, PDE-200, NOF Corporation)
as a cross-linker were added to a 16 wt % aqueous solution of
poly[NIPAAm-co-Ru(bpy)
3
-co-AMPS] (0.64 g). The solution
was injected between glass plates separated by a silicone spacer
(thickness = 0.5 mm) and then left to polymerize for 18 h at 60
C. The resulting semi-IPN BZ gel was soaked in pure H
2
O for
2 weeks to remove unreacted monomer.
Synthesis of the Conventional BZ Gel. The monomers
NIPAAm (0.78 g), AMPS (27.6 mg), and Ru(bpy)
3
(81.3 mg)
were dissolved in ethanol/H
2
O (1:1 w/w) to give a total
monomer concentration of 16 wt %, and azobisisobutyronitrile
(AIBN) (33.3 mg) and N,N-methylenebisacrylamide
(MBAAm) (14.0 mg) were added as the initiator and the
cross-linker in the monomer solution. To synthesize the gel,
this solution was injected between two glass plates separated by
a silicone spacer (thickness = 0.5 mm), and then radical
polymerization was allowed to proceed for 20 h at 60 C. The
resulting gel membrane was soaked in pure ethanol for 1 week
to remove unreacted monomer and then gradually hydrated by
sequential immersion in decreasing concentrations of ethanol in
H
2
O (75%, 50%, 25%, and 0%) for 1 day each.
Measurements of the BZ Reaction in Gels. The gel
membranes were immersed in an aqueous solution including
MA and NaBrO
3
. The resulting BZ reactions were observed
and recorded using a microscope (WAT-250D, Fortissimo
Corp, Tokyo, Japan) and a video recorder (SR-DVM700,
Victor Corp., Yokohama, Japan). The moving image was
subjected to redgreenblue (RGB) analysis.

RESULTS AND DISCUSSION

Table 1 summarizes the occurrence and periods of oscillations
in the semi-IPN BZ gel in the presence of dierent
concentrations of sodium bromate (NaBrO
3
) and malonic
acid (MA), at a xed temperature of 20 C. The data indicate
that the BZ reaction in the semi-IPN BZ gel occurred when the
NaBrO
3
concentration was higher than 0.6 M; a MA
concentration higher than 0.8 M was required when the
NaBrO
3
concentration was 0.6 M. The semi-IPN BZ gel
required higher concentrations of NaBrO
3
and MA than that
required in the initial BZ gel.
35,36
The requirement of higher concentrations of NaBrO
3
and
MA for the BZ reaction when strong acids were not directly
added is explained by the FieldKorosNoyes (FKN)
mechanism.
37,38
According to the FKN mechanism, the BZ
reaction is divided into three main processes: consumption of
Br

ions (process A), autocatalytic formation of HBrO

2
(process B), and formation of Br

ions (process C)
process A
+ +
+
BrO 2Br 3H 3HOBr
3
process B
+ + +
+ +
+
BrO HBrO 2M 3H
2HBrO 2M H O
3 2 red
2 ox 2
Table 1. Phase Diagram of the Oscillating Region Given by
the Initial Concentrations of NaBrO
3
and MA at a Fixed
Temperature (20 C)
a
[NaBrO
3
] (M)
[MA]
(M) 0.2 0.4 0.6 0.8 1.0 1.2 1.4
0.2
(94 s)

(63 s)

(64 s)
0.4
(50 s)

(63 s)

(50 s)

(47 s)
0.6
(29 s)

(43 s)

(33 s)
0.8
(51 s)

(27 s)

1.0
(47 s)

(29 s)

(30 s)

(35 s)

a
Numbers in parentheses denote oscillation periods; crosses indicate
no oscillation.
The Journal of Physical Chemistry B Article
dx.doi.org/10.1021/jp410915p | J. Phys. Chem. B 2014, 118, 634638 635
process C
+ + + +

f 2M MA BrMA Br 2M other products

ox red
Processes B and C are catalyzed by Ru(bpy)
3
; the reduced form
of Ru(bpy)
3
is oxidized during process B, and the oxidized form
is reduced during process C. For processes A and B to proceed
without strong acids, a high concentration of NaBrO
3
is
required to compensate for the lower concentration of H
+
. At
NaBrO
3
concentrations of 0.6 and 0.8 M, the minimum
amounts of MA necessary for the BZ reaction to occur in the
gel were found to be higher than when the NaBrO
3
concentration was 1.0 M (Table 1). The mole fraction of
oxidized Ru(bpy)
3
(M
ox
) was lower in process B; this was
attributed to the decrease in the reaction rate because of the
low concentration of H
+
. In contrast, in process C, the low
concentration of M
ox
necessitated a high concentration of MA
at NaBrO
3
concentrations of 0.6 and 0.8 M, resulting in the
occurrence of the BZ reaction only at high MA concentrations.
As shown in Table 1, the period of the BZ reaction decreased
with increasing concentration of MA. Figure 1A shows the RGB
analysis of the BZ reaction in semi-IPN BZ gels. Figure 1B
shows a logarithmic plot of the oscillation period against the
initial concentration of MA at a xed concentration of NaBrO
3
(1.0 M). The data were tted to a linear equation. The period
of self-oscillation can be expressed as a[substrate]
b
, where a and
b are experimental constants and the square brackets indicate
the initial substrate concentration. This result indicates that the
oscillation period of the BZ reaction in the semi-IPN BZ gel
was similar to that in the normal self-oscillating polymer system
at high concentrations of H
+
.
39
Figure S1 (Supporting Information) shows a schematic
illustration of the setup of the adhesion experiment without
strong acids. By pressing the silicone rubber, the two gels were
connected. Figure 2 shows the results of the RGB analysis for
the semi-IPN and conventional BZ gels in the connected
(Figure 2A) and disconnected (Figure 2B) states. The chemical
waves in the semi-IPN BZ gel and the conventional BZ gel
were analyzed using the green and red values, respectively,
because the colors of these gels were quite dierent. It is
evident from the gure that, when the two types of gels were
connected, the BZ reaction was observed in the conventional
BZ gel without strong acids; in other words, the semi-IPN BZ
gel switched on the BZ reaction in the conventional BZ gel. In
the disconnected state, the reaction was switched o in the
conventional BZ gel, demonstrating that the semi-IPN BZ gel
controlled the BZ reaction (Figure 2B). Thus, the ono
switching of the BZ reaction of the conventional BZ gel can be
controlled without strong acids. This switching mechanism of
the BZ reaction in the gel has important applications in the
development of chemical actuators and robots. In addition, as
shown in Figure 2A, the periods of self-oscillation for the two
types of gels are quite dierent. The oscillation period is
determined by the concentration of the reactive substrates of
the BZ reaction. In the conventional BZ gel, no intermediate
substrates were produced; therefore, the period of oscillation in
this gel was much longer than that in the semi-IPN BZ gel.
Figure 1. (A) RGB analysis of the semi-IPN BZ gel ([NaBrO
3
] = 1.2
M, [MA] = 0.6 M). (B) Logarithmic plot of period (t in seconds) vs
initial concentration of MA at [NaBrO
3
] = 1.0 M.
Figure 2. RGB analysis of the (A) connected and (B) disconnected
gels ([NaBrO
3
] = 1.0 M, [MA] = 0.5 M).
The Journal of Physical Chemistry B Article
dx.doi.org/10.1021/jp410915p | J. Phys. Chem. B 2014, 118, 634638 636
As a control, a conventional BZ gel was placed in the same
solution (see Figure S1, Supporting Information). Figure 3
shows the results of the RGB analysis for the control gels; no
oscillations in either red or green can be seen. The results
indicate that, when the two gels were connected to each other,
the reactive intermediates of the BZ reaction produced in the
semi-IPN BZ gel propagated into the conventional BZ gel.
However, no intermediates were formed in the disconnected
conventional BZ gel; therefore, the BZ reaction was not
observed when strong acids were not directly added (Figures
2B and 3A,B). As indicated by the FKN mechanism, a high
concentration of H
+
is required for the intermediate processes
of the BZ reaction to proceed. These results explain the
occurrence of the BZ reaction in the conventional BZ gel when
it was in physical contact with the semi-IPN BZ gel.

CONCLUSIONS
The novel gel system developed in this work facilitated the BZ
reaction when strong acids were not directly added. The high
concentrations of the two BZ substrates compensated for the
low concentration of H
+
; the periods of the BZ oscillation
decreased with the increase in the concentrations of the
substrates. Moreover, the BZ reaction in the conventional gel
was initiated and terminated by connecting to and disconnect-
ing from the semi-IPN BZ gel, respectively. This is the rst
demonstration of the ono switching of the BZ reaction
without strong acids, controlled by the physical contact
between two gels.

ASSOCIATED CONTENT
*S Supporting Information
Schematic illustration of the setup of the adhesion experiment
in acid-free conditions. This material is available free of charge
via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION
Corresponding Author
*E-mail: y-hara@aist.go.jp. Phone: +81-29-861-9318. Fax: +81-
29-861-6236.
Notes
The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
This work was carried out with nancial aid from the Industrial
Technology Research Grant Program, 2011, sponsored by the
New Energy and Industrial Technology Development Organ-
ization (NEDO), Japan. This work was also supported by
Grants-in-Aid (KAKENHI) for Challenging Exploratory
Research (24656178) and Scientic Research on Innovative
Area (25104501) from the Ministry of Education, Culture,
Sports, Science, and Technology, Japan (MEXT).

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