Experimental

Synthesis of Colloidal Crystals as Templates: To prepare the closest-packed

colloidal crystals, a 15 wt.-% aqueous solution of silica spheres, having a diameter of 291 nm as determined from SEM measurements, was used. The growth of
the crystal by the gravity sedimentation method was conducted in a flat Petri
dish at 20 C. The stable dried crystals were obtained within 1 week as the water
evaporated, and then completely dried in vacuo at 60 C. It is generally accepted that the crystalline arrays produced by the gravity sedimentation method have a cubic close-packed structure containing polycrystalline domains, similar to that of a natural opal. The thickness of the crystal can be easily controlled
by the colloidal concentration and the iterative treatment. On the other hand,
fine ordered crystals were created by the solvent evaporation method as follows: the colloidal suspension (ca. 15 wt.-%) was dropped onto a clean microscope slide and was placed in a thermostatic chamber at 90 C, in which the solvent gradually evaporated. A high quality crystal can be prepared with a
thickness of up to 1 mm.
Synthesis of Porous Hydrogels and Cylindrical Hydrogels: The thermosensitive gels were prepared by free-radical polymerization as follows. First, N-isopropylacrylamide (NIPA, 11.3 g), N, N-methylene bis(acrylamide) (0.513 g) as
a crosslinker, and benzoylperoxide (0.048 g), the initiator, were dissolved in
degassed and nitrogen-saturated 1,4-dioxane to a final volume of 50 mL. The
solution was then infiltrated into the colloidal crystals in a Petri dish, and the
polymerization was conducted at 60 C for 40 h. Afterwards, the samples were
immersed in a 5 wt.-% HF aqueous solution to remove the SiO2. The gels for a
swelling measurement were prepared in micropipettes of 100 lm diameter. The
resulting porous gels and the cylindrical gels were washed carefully with distilled water for 1 week.
Measurements: The swelling measurement was carried out by monitoring the
diameter of the cylindrical gel in water. The temperature was controlled by
using a temperature control system with circulating water. The reflection spectra were obtained by an Ocean Optics USB2000 fiber optic spectrometer
Received: September 9, 2002
Final version: November 5, 2002

[1] G. Vlatakis, L. I. Anderson, R. Mller, K. Mosbach, Nature 1993, 361,

645.
[2] V. T. Remcho, Z. J. Tan, Anal. Chem. 1999, 71, 248A.
[3] C. Alvarez-Lorenzo, O. Guney, T. Oya, Y. Sakai, M. Kobayashi, T. Enoki,
Y. Takeoka, T. Ishibashi, K. Kuroda, K. Tanaka, G. Wang, A. Y. Grosberg,
S. Masamune, T. Tanaka, Macromolecules 2000, 33, 8693.
[4] C. Alvarez-Lorenzo, O. Guney, T. Oya, Y. Sakai, M. Kobayashi, T. Enoki,
Y. Takeoka, T. Ishibashi, K. Kuroda, K. Tanaka, G. Wang, A. Y. Grosberg,
S. Masamune, T. Tanaka, J. Chem. Phys. 2001, 114, 2812.
[5] T. Enoki, K. Tanaka, T. Watanabe, T. Oya, T. Sakiyama, Y. Takeoka,
K. Ito, G. Wang, M. Annaka, K. Hara, R. Du, J. Chuang, K. Wasserman,
A. Y. Grosberg, S. Masamune, T. Tanaka, Phys. Rev. Lett. 2000, 85, 5000.
[6] L. Liu, P. Li, S. A. Asher, Nature 1998, 397, 141.
[7] Y. Takeoka, M. Watanabe, Langmuir 2002, 18, 5977.
[8] P. Jiang, J. F. Bertone, K. S. Hwang, V. L. Colvin, Chem. Mater. 1999, 11,
2132.
[9] L. N. Donselaar, A. Philipse, J. Suurmond, Langmuir 1997, 13, 6018.
[10] H. Miguez, F. Meseguer, C. Lopez, A. Misfsud, J. S. Moya, L. Vazquez,
Langmuir 1997, 13, 6009.
[11] S. H. Park, Y. Xia, Langmuir 1999, 15, 266.
[12] Y. Hirokawa, T. Tanaka, E. S. Matsuo. J. Chem. Phys. 1984, 85, 6379.
[13] We did not use a macroporous gel to determine the swelling behavior.
Therefore, a small difference in swelling size between the porous gel and
cylindrical gel seems to be present, because the quantitatively different
values were obtained in the wavelength of the peak of the reflection spectra from a porous gel as a function of temperature in Fig. 4b. Nevertheless,
the experimental results qualitatively prove our description.

Adv. Mater. 2003, 15, No. 3, February 5

Anisotropic Bending and Unbending Behavior

of Azobenzene Liquid-Crystalline Gels by Light
Exposure
By Tomiki Ikeda,* Makoto Nakano, Yanlei Yu,
Osamu Tsutsumi, and Akihiko Kanazawa
Photoresponsive liquid-crystalline (LC) polymers have
been extensively explored recently as highly functional and
high-performance materials in information technology fields,
because of their large anisotropy in optical and other physical
properties.[15] In particular, cross-linked polymer LCs (PLCs)
have attracted much attention for LC gels (LCGs) or LC networks (LCNs) due to their specific properties arising from the
cross-linked polymer and LC behavior.[49]
Polymer gels may deform in response to a variety of external stimuli such as temperature, pH, ionic strength, electric
field, and light.[1012] Several successful examples have been
reported on photoresponsive gels, such as volume phase transitions in N-isopropylacrylamide (NIPA)-based gels induced
by light.[1315] Mamada et al.[13] observed that the incorporation of triphenylmethyl moieties into the NIPA-based gel enabled the gel to expand in water by irradiation. However, the
volume phase transition in those gels is due to the change in
the osmotic pressure by the external stimuli, and the rate-determining step of the deformation is the diffusion process.
Therefore, the response is too slow for various applications.[16]
Gels containing azobenzenes can expand or contract due to
photoinduced structural changes of the azobenzenes. Upon
photoirradiation, azobenzenes show transcis isomerization
and exhibit a large change in the molecular length: the distance between 4- and 4-carbons decreases from 9.0 (trans)
to 5.5 (cis).[17] Eisenbach reported that polymers crosslinked with azobenzenes contract upon UV irradiation. However, the observed contraction was very small (0.15
0.25 %).[18] Recently, de Gennes et al. reported on theoretical
studies on the possibility of a large deformation of LCGs,[16]
and several groups demonstrated experimentally large deformations of LCNs induced by an electric field or temperature.[19,20] Finkelmann et al. reported a pioneering work on
large contractions of LCNs containing azobenzene moieties
by light.[21] Although their LCNs show excellent properties in
comparison to previous LCGs or LCNs, there still remain
some problems to be addressed for practical applications, i.e.,
response time and the type of deformation.
To prepare LCGs and LCNs showing large deformations
and fast response, we focused our attention on LCGs and

[*]

Prof. T. Ikeda, Dr. M. Nakano, Y. Yu, Dr. O. Tsutsumi,

Prof. A. Kanazawa[+]
Chemical Resources Laboratory
Tokyo Institute of Technology
4259 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan)
E-mail: [email protected]

[+]

Present address: Department of Polymer Science and Engineering,

Faculty of Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa,
Yamagata 992-8510, Japan.

2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

0935-9648/03/0302-0201 $ 17.50+.50/0

201

COMMUNICATIONS

crosslinker are controlled, it is technically possible to prepare

a gel membrane reflecting the specific color at a certain temperature. This method to prepare the interconnecting porous
gels will give us the potential to study appropriate smart gels
that may have interesting applications, such as in tunable optical filters, actuators, and sensors. Studies to confirm this are
underway.

COMMUNICATIONS

LCNs composed only of azobenzene moieties. In previous

studies, we found that the photoresponse of the PLCs consisting only of azobenzene moieties is much faster than that of
copolymers composed of azobenzenes and non-photoactive
mesogens.[3a] Therefore, it is expected that LCGs and LCNs
composed only of azobenzene mesogens undergo fast deformation. Furthermore, in these LCGs and LCNs, due to large
extinction coefficients of the azobenzene moiety, the depth
profile for absorption of photons can be controlled just by
choosing a suitable wavelength of actinic light. For instance, if
absorption of photons occurs only in the surface of the film
and transcis photoisomerization takes place only in the surface area, a bilayer structure with slabs of two different polymers that respond differently can be obtained; bending
could then be induced, like in a bimetal. Since this mode of
deformation is very advantageous for an artificial hand,
LCGs or LCNs that show bending upon photoirradiation are
suitable for light-driven actuators. Furthermore, since only a
part of the LCG or LCN is involved in the deformation in
these materials, the bending could be much faster than other
modes of deformation. Here, we report anisotropic bending
and unbending of LCGs and LCNs induced by light.
The cross-linked polymer films were prepared by in-situ
photopolymerization of an LC monomer containing an azobenzene moiety (1) and a diacrylate with an azobenzene moiety (2) at various ratios of 1 to 2 (Fig. 1). The cross-linked
polymer films prepared with a high concentration of the
cross-linking agent (20 mol-%) showed a glass transition temperature (Tg) at 85 C and a LC phase up to 300 C. The alignment of the azobenzene moieties in the cross-linked polymer
films was examined by polarized UV-vis and IR absorption
spectroscopy. It was revealed that the azobenzene moieties
are preferentially aligned along the rubbing direction of the
alignment layer in the cell used for the preparation of the
cross-linked films. The cross-linked polymer films showed a
swelling in good solvents, such as toluene and chloroform,
but little change in size in poor solvents such as methanol and
n-hexane, as shown Figure 1b. In addition, the swelling of the
LCG films was anisotropic in good solvents: the enlargement
of the LCG films was larger by a factor of 1.4 in the direction
parallel to the rubbing direction of the alignment layer than in
the direction perpendicular to the rubbing direction.
Exposure of the LCG film in toluene to UV light at
360 nm, which causes transcis photoisomerization of the
azobenzene moieties, brought about bending of the LCG film
towards the irradiation direction of the actinic light as shown
in Figure 2a. Here, the LCG film was prepared from a mixture of 1 (80 mol-%) and 2 (20 mol-%) in the presence of
2 mol-% of the photoinitiator. At a light intensity of
3 mW cm2, the bending was completed in 20 s. When the
bent film was exposed to visible light at 450 nm, which causes
cistrans back isomerization of the azobenzene moiety,
unbending of the LCG film immediately took place and the
initial flat film was restored in 30 s at the same light intensity.
This bending and unbending of the LCG films could be re-

202

2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Fig. 1. Structures of the azobenzene LC monomers used in this study and anisotropic swelling of the LCG film. a) Structures of the azobenzene LC monomers.
b) Anisotropic swelling of the LCG film in methanol (a poor solvent) and toluene (a good solvent). c) Schematic illustrations for the anisotropic swelling of
the LCG film in methanol and toluene. The LCG film was prepared from a mixture of A6AB6 (90 mol-%) and DA6AB (10 mol-%) containing 2 mol-% of a
photoinitiator. The swelling in the good solvent was anisotropic: more enlargement of the LCG films was observed in the direction parallel to the rubbing
direction of the alignment layer of the cells.

peated just by changing the wavelength of the irradiation

light. It is worth mentioning here that the bending of the LCG
films occurred only in the direction parallel to the rubbing
direction of the polyimide alignment layer of the cell, and did
not take place in other directions.
The optical properties of the LCG film during the bending
and unbending processes were also examined by polarizing
microscopy. It was clearly observed that the LCG film showed
optical anisotropy at all stages of the bending and unbending
processes (Fig. 2b). This means that the bending and unbending occur in the anisotropic phases.
These responses are different from the photoresponsive
behavior of the LCNs reported by Finkelman et al. in two aspects.[21] First, the response of the present LCGs is faster by

0935-9648/03/0302-0202 $ 17.50+.50/0

Adv. Mater. 2003, 15, No. 3, February 5

Adv. Mater. 2003, 15, No. 3, February 5

2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

0935-9648/03/0302-0203 $ 17.50+.50/0

203

COMMUNICATIONS

oriented, and found that bending and unbending of the gels took place to some extent in toluene, but they were incomplete
and isotropic; there was no preferential direction in bending.
Bending and unbending were observed in
good solvents, such as toluene and chloroform, but not induced in poor solvents such
as methanol and n-hexane. Interestingly,
the cross-linked LC polymer films showed a
bending toward the irradiation direction
even in air (in the absence of any solvent),
when the films were heated to 90 C, which
is above the Tg of the films as shown in Figure 3. The response of the cross-linked LC
polymer films for bending in air was also
fast: the bending was completed in 80 s and
the bent film was restored to the initial
flat film in 90 s. These findings seem to rule
out the possibility that the bending of
the LCG films is caused by the shrinkage
of the slab of the polymer with cis-azobenzene moieties due to exclusion of solvent
molecules, arising from the increased polarity of the azobenzene. In good solvents,
the LCG films are swollen, which enables
the azobenzene moieties to isomerize efficiently due to increases in free volume and
segmental mobility of the polymers. These
requirements could be fulfilled if the
cross-linked LC polymer films are heated
above Tg.
The mechanism of the photoinduced
bending is thought to be as follows
(Fig. 4). The thickness of the cross-linked
LC polymer film is typically 10 lm. The
extinction coefficient of the azobenzene
moieties at 360 nm is large (2.6
104 L mol1 cm1) and 99 % of the incident
Fig. 2. Bending and unbending behavior of the LCG film in toluene. The LCG film was prepared from
a mixture of 1 (80 mol-%) and 2 (20 mol-%) containing 2 mol-% of a photoinitiator. The LCG film
photons are absorbed by the surface withbent toward the irradiation direction of UV light (360 nm) and reverted to the initial flat film comin a thickness of < 1 lm. This means that
pletely upon irradiation of visible light (450 nm). The bending was always induced in one direction: the
upon photoirradiation at 360 nm, the
rubbing direction of the alignment layer of the cells used for the preparation of the LCG films.
a) Photographs taken during bending and unbending processes. b) Polarizing micrographs observed
transcis photoisomerization occurs only
during the bending and unbending processes. The LCG film showed optical anisotropy at all stages of
in the surface region, and in the bulk of
the bending and unbending processes. c) Schematic illustration for anisotropic bending and unbending
behavior of the LCG film.
the film the trans forms of the azobenzene
remain unchanged. In other words, the
volume contraction is induced only in the
surface region of the cross-linked LC polymer film upon
about two orders of magnitude than that of their LCNs
irradiation. Therefore, the bending is induced toward the
(90 min). This may be understood in terms of a different
incident direction of the actinic light. Furthermore, since
mechanism of response of the present LCGs. Second, the
the azobenzene moieties are aligned into one direction in
mode of deformation is quite different between these two
the cross-linked films, the films could contract only in one
materials, i.e., contraction in LCNs by Finkelmann et al. and
direction upon transcis photoisomerization. Thus, the freebending by us.
standing cross-linked LC polymer films undergo an anisoAs a control experiment, we examined the photoresponsive
tropic bending. For the bending and unbending of the crossbehavior of isotropic gels made of 4-(phenylazo)phenyl acrylinked LC polymer films to be induced, the relaxation of
late (3) and 2, in which azobenzene moieties are randomly

COMMUNICATIONS
Fig. 3. Bending and unbending behavior of the LCN film at 90 C in air. The LCN film bent toward the irradiation direction of UV light (366 nm) and reverted
to the initial flat film completely upon irradiation of visible light (450 nm). The bending was always induced along the rubbing direction of the cell. A part of the
film was fixed (pasted) on a glass substrate and irradiated. a) The rubbing direction is perpendicular to one side of the glass substrate. b) Schematic illustration
of anisotropic bending and unbending behavior in (a). c) The rubbing direction is parallel to one side of the glass substrate. d) Schematic illustration for anisotropic bending and unbending behavior in (c). In (c), upon UV irradiation, the film was broken by bending along the rubbing direction.

polymer segments is necessary, which could be achieved by

suspending the film into solvents or heating it to above Tg.
The origin of the bending is an unbalanced contraction

204

2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

between the surface area and the bulk of the material.

These photoresponsive materials enable light energy to be
converted into specific mechanical work.

0935-9648/03/0302-0204 $ 17.50+.50/0

Adv. Mater. 2003, 15, No. 3, February 5

Experimental
Preparation of the sample: The azobenzene LCG films were prepared by insitu photopolymerization of an LC monomer containing an azobenzene moiety
(1) and a diacrylate with an azobenzene moiety (2) at various ratios of 1 and 2
(mol-%) (90:1080:20). Both monomers were synthesized according to the
method reported previously [22]. The mixture containing a photoinitiator (Ciba
Specialty, Irgacure 784; 2 mol-%) was injected into a glass cell with polyimide
alignment layers at 100 C (in an isotropic phase). It was confirmed that the
photoinitiator did not destabilize the LC phase at this concentration and no
spontaneous thermal polymerization occurred during injection of the LC monomers into the cell. After the mixture in the cell was cooled down slowly
(0.5 C min1) to a polymerization temperature (85 C), photoirradiation at
> 540 nm (1.9 mW cm2 at 547 nm) was performed with a 500 W high-pressure
mercury lamp through glass filters (Toshiba, Y-52 + IRA-25) for 2 h. After polymerization, the cross-linked polymer film was taken off from the cell and
washed thoroughly with chloroform to completely remove unreacted monomers. Finally, the cross-linked polymer film was dried under reduced pressure
to remove the solvent.
Bending behavior in solvents: The cross-linked polymer films were cut into
rectangular sections (1.3 mm 0.8 mm 10 lm), and placed horizontally in a
vessel containing toluene (Fig. 2c). These LCG films were irradiated at room
temperature at 360 nm from a Xe lamp (obtained through a monochromator
(JASCO SM-5)). The bent films were exposed to visible light at 450 nm from
the Xe lamp (obtained through the monochromator). The actinic light was irradiated from 4 cm above part of the film). The deformation behavior was observed by polarizing microscopy (Olympus BH-2) at room temperature.
Bending behavior in air: To explore the bending behavior of the cross-linked
LC polymer films, the films were cut into rectangular shape (1 mm
0.6 mm 10 lm; in some cases 5 mm 5 mm 20 lm), and about one-third to
one-half of the film was pasted to a glass substrate (Fig. 3c). The glass substrate
with a film was placed on a hot stage (Mettler FP82HT and Mettler FP90), and
kept at 90 C (above Tg). Then the film was irradiated at 366 nm from a 500 W
high-pressure mercury lamp through glass filters (Toshiba, UV-D36A + UV35 + IRA25-S). The actinic light was irradiated from above, 4 cm away from the
film.

By Dayang Wang and Frank Caruso*

Three-dimensional (3D), ordered macroporous materials
with pore sizes in the submicrometer to micrometer range are
of significant interest because of their application in separation processes,[1a] as light-weight structural materials,[1b] as
catalytic supports and surfaces,[1c] as thermal and acoustic
insulators,[1d] and as low-dielectric materials.[1e] Such materials
have also received intense interest because of their importance in photonics,[2] where they can be used as photonic crystals for the manipulation of electromagnetic waves, for example, by localizing light and controlling spontaneous
emission.[3]
The use of colloidal crystals as templates has proven to be a
promising approach for the fabrication of 3D, highly ordered
macroporous materials, or inverse opals.[4] Inverse opals are
comprised of air spheres that are close-packed in a highly ordered 3D array, and are interconnected to each other by small

[*] Prof. F. Caruso,[+] Dr. D. Wang

Max Planck Institute of Colloids and Interfaces
D-14424 Potsdam (Germany)

Received: April 25, 2002

Final version: December 4, 2002

[+] Present address: Department of Chemical and Biomolecular Engineering,

The University of Melbourne, Victoria 3010, Australia.
E-mail: [email protected]

M. Eich, J. H. Wendorff, Makromol. Chem. Rapid Commun. 1987, 8, 59.

T. Fischer, L. Lasker, M. Rutloh, S. Czapla, J. Stumpe, Mol. Cryst. Liq.
Cryst. 1997, 299, 293.

[**] D. W. acknowledges the Alexander von Humboldt Foundation for a Research Fellowship. This work was funded by the BMBF, the Volkswagen
Foundation, and the DFG. H. Mhwald is thanked for supporting this
work within the MPI.

[1]
[2]

Lithium Niobate Inverse Opals Prepared

by Templating Colloidal Crystals
of Polyelectrolyte-Coated Spheres**

Adv. Mater. 2003, 15, No. 3, February 5

2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

0935-9648/03/0302-0205 $ 17.50+.50/0

205

COMMUNICATIONS

Fig. 4. Schematic illustration of the mechanism of the bending.

[3] a) T. Ikeda, O. Tsutsumi, Science 1995, 268, 1873. b) Y. Wu, T. Ikeda,

Q. Zhang, Adv. Mater. 1999, 11, 300. c) M. Hasegawa, T. Yamamoto,
A. Kanazawa, T. Shiono, T. Ikeda, Adv. Mater. 1999, 11, 675.
[4] a) S. Kurihara, A. Sakamoto, T. Nonaka, Macromolecules 1998, 31, 4648.
b) S. Kurihara, A. Sakamoto, D. Yoneyama, T. Nonaka, Macromolecules
1999, 32, 6493. c) S. Kurihara, D. Yoneyama, T. Nonaka, Chem. Mater.
2001, 13, 2807.
[5] Y. Zhao, S. Bai, D. Dumont, T. V. Galstian, Adv. Mater. 2002, 14, 512.
[6] H. Finkelmann, H. R. Brand, Trends Polym. Sci. 1994, 2, 222.
[7] D. J. Broer, I. Heynderickx, Macromolecules 1990, 23, 2474.
[8] R. A. M. Hikmet, J. Mater. Chem. 1999, 9, 1921.
[9] M. Trollss, C. Orrenius, F. Sahln, U. W. Gedde, T. Norin, A. Hult,
D. Hermann, P. Rudquist, L. Komitov, S. T. Lagerwall, J. Lindstrm,
J. Am. Chem. Soc. 1996, 118, 8542.
[10] T. Tanaka, Phys. Rev. Lett. 1978, 40, 820.
[11] R. A. Siegel, B. A. Firestone, Macromolecules 1988, 21, 3254.
[12] T. Tanaka, I. Nishio, S.-T. Sun, S. Ueno-Nishio, Science 1982, 218, 467.
[13] A. Mamada, T. Tanaka, D. Kungwatchakun, M. Irie, Macromolecules
1990, 23, 1517.
[14] A. Suzuki, T. Tanaka, Nature 1990, 346, 345.
[15] J. Zhang, Y. Li, Z. Hu, C. L. Littler, J. Chem. Phys. 1995, 102, 551.
[16] P.-G. de Gennes, M. Hbert, R. Kant, Macromol. Symp. 1997, 113, 39.
[17] S. Xie, A. Natansohn, A. P. Rochon, Chem. Mater. 1993, 5, 403.
[18] C. D. Eisenbach, Polymer 1980, 21, 1175.
[19] W. Lehmann, H. Skupin, C. Tolksdorf, E. Gebhard, R. Zentel, P. Krger,
M. Lsche, F. Kremer, Nature 2001, 410, 447.
[20] D. L. Thomsem III, P. Keller, J. Naciri, R. Pink, H. Jeon, D. Shenoy, B. R.
Ratna, Macromolecules 2001, 34, 5868.
[21] H. Finkelmann, E. Nishikawa, G. G. Pereira, M. Warner, Phys. Rev. Lett.
2001, 87, 15 501.
[22] A. Angeloni, D. Caretti, C. Carlini, E. Chilellini, G. Galli, A. Altomare,
R. Solao, M. Laus, Liq. Cryst. 1989, 4, 513.