910 Langmuir 1999, 15, 910-913

Inclusion Complex Formation of Cyclodextrin and

Polyaniline
Ken-ichi Yoshida, Takeshi Shimomura, Kohzo Ito,* and Reinosuke Hayakawa
Department of Applied Physics, Graduate School of Engineering, University of Tokyo, Hongo,
Bunkyo-ku, Tokyo 113-8656, Japan
Received September 14, 1998. In Final Form: December 7, 1998

Inclusion complex formation between polyaniline with emeraldine base and β-cyclodextrin has been
studied by the frequency-domain electric birefringence (FEB) spectroscopy in a solution of N-methyl-2-
pyrrolidone (NMP) and by scanning tunneling microscopy (STM). The FEB results show that polyaniline
in the solution with cyclodextrin changes its conformation from coil to rod at low temperature (below 275
K), and some rodlike images are observed on a substrate by STM. These results suggest that cyclodextrins
are threaded onto polyaniline and confine the conformation of the polymer chain to a rodlike one.
Furthermore, it is found that the threaded cyclodextrins prevent the chemical oxidation, i.e., doping of
polyaniline by iodine. This indicates formation of a new inclusion complex, a conjugated conducting polymer
covered by insulated cyclic molecules, namely, “insulated molecular wire”.

Introduction
Much attention has been recently focused on the design
of nanometer-scale (nanoscale) molecular devices. One
approach to the molecular devices is the self-assembly of
supramolecular structures such as inclusion complexes.1,2
Cyclodextrins (CDs) are cyclic molecules which consist
of six to eight glucose units: R-, β-, and γ-cyclodextrins
with six, seven, and eight glucose units, respectively
(Figure 1a). Their cylindrical structures with cavities of
about 0.7 nm deep and 0.5-0.8 nm inside diameter yield
various unique properties. In particular, CDs form inclu-
sion complexes with various low molecular weight com-
pounds by including them into the cavities.1
Recently, it was reported that many CDs were threaded
onto a polymer chain and formed an inclusion complex
named a “molecular necklace”.1,3 Such a structure confines
the conformation of the polymer chain to a rodlike one (all
trans configuration) owing to very small cavities and close
packing of the CD molecules. Hence the inclusion complex
formation between CDs and a polymer chain is entropically
unfavorable and encouraged at low temperature by
noncovalent interaction such as hydrophobic one, similarly
to the inclusion complex formation between linear polymer
chains and molecular nanotubes synthesized through the
molecular necklace.4
In this paper, our aim is to study inclusion complex
formation between these cyclic molecules and conjugated
conducting polymers by frequency-domain electric bire-
fringence (FEB) spectroscopy and by scanning tunneling
microscopy (STM). Since the FEB signal, or the Kerr effect,
comes from optical and electrical anisotropy of molecules,
rodlike molecules such as liquid crystals, tobacco mosaic
virus, polypeptides, and linear polyions yield large electric
birefringence but isotropic molecules such as coiled
Figure 1. Schematic diagrams of (a) cyclodextrins, (b) poly-
polymer chains and spherical latices exhibit no signal.5 aniline with emeraldine base, and (c) inclusion complex
Thus the FEB technique is a useful tool to determine formation of cyclodextrins and a conducting polymer chain:
insulated molecular wire.
* To whom correspondence should be addressed.
(1) Wenz, G. Angew. Chem., Int. Ed. Engl. 1994, 33, 803.
(2) Philp, D.; Stoddart, J. F. Angrew. Chem., Int. Ed. Engl. 1996, 35, whether the conformation of a polymer chain is rodlike or
1155. coiled in solution. In practice, we have investigated the
(3) Harada, A.; Li, J.; Kamachi, M. Nature 1992, 356, 325; Macro- rod-coil transition of a conjugated conducting polymer in
molecules 1994, 27, 4538.
(4) Okumura, Y.; Ito, K.; Hayakawa, R. Phys. Rev. Lett. 1998, 80,
solution by FEB.6 As schematically shown in Figure 1c,
5003.
(5) O’Konski, C. T. Molecular Electrooptics: Part 1; Marcel Dekker: (6) Shimomura, T.; Sato, H.; Furusawa, H.; Kimura, Y.; Okumoto,
New York, 1976. H.; Ito, K.; Hayakawa, R.; Hotta, S. Phys. Rev. Lett. 1994, 72, 2073.

10.1021/la9812471 CCC: $18.00 © 1999 American Chemical Society

Published on Web 01/20/1999
Letters
it is expected that the inclusion complex formation between
CDs and a conducting polymer changes the polymer
conformation from coiled to rodlike in solution. Then we
can detect the appearance of rodlike polymer chains with
high sensitivity by FEB. In this study, we adopt β-CD as
a cyclic molecule and polyaniline (PAn) (Figure 1b) as a
soluble conducting polymer since it is known that aniline,
the monomer of PAn, forms inclusion compounds with
β-CD, not R-CD.7,8 The inclusion complex between β-CD
and PAn can be regarded as a novel kind of molecular
devices: a conjugated conducting polymer covered by
insulated cyclic molecules. Very recently, such insulated
molecular wire has been synthesized by coupling several
threaded conjugated monomer units.9 The present insu-
lated molecular wire is about thousand times as long as
the previous one.
Experimental Section
We purchased β-CD, N-methly-2-pyrrolidone (NMP) as
a solvent and iodine as a dopant from Nacalai Tesque and
used them without further purification. Polyaniline (PAn)
with emeraldine base, synthesized by chemical oxidative
polymerization of aniline, was supplied by Nitto Denko
Co. A weight-average molecular weight Mw and the
polydispersity ratio Mw/Mn of PAn were evaluated as 6.2
× 104 and 8.5, respectively, by gel permeation chroma-
tography (GPC).
In the FEB method, we apply the sinusoidal electric
field E ) Re[E0 exp(iωt)] with the angular frequency of ω
and the amplitude of E0 to the specimen and detect the
birefringence signal ∆n of the solution. If the applied field
orients molecules in the solution and the molecules have
optical anisotropy, the solution exhibits birefringence,
which is called the Kerr effect as a second-order nonlinear
optical effect. By FEB, we obtain the frequency-dependent
Kerr constant K ≡ ∆n/E02 ) Kdc+ Re[K2ω* exp(i2ωt)] where
Kdc corresponds to the dc component and K2ω* ()K2ω′ -
iK2ω′′) is the complex amplitude of the 2ω component.
According to the theoretical treatment,10 Kdc (≡Re[ψ*])
affords the information on the anisotropy and dynamics
of the electrical polarizability of the polymer chain while
K2ω* is given by K2ω* ) ψ* [1 + i(2/3)ωτr]-1 with the
rotational relaxation time τr. It is to be noted that the
FEB response appears only in solutions of rodlike mol-
ecules which have electro-optical anisotropy. We measured
the FEB spectra in the temperature range of 250-300 K.
The outline of the apparatus was reported in the previous
paper.10
STM was performed with NanoscopeII (Digital Instru-
ments) in air using Pt-Ir tips in a constant height mode.
The sample was prepared by spin-coating a drop of the
solution cooled at 255 K onto fleshly cleaved highly
oriented pyrolytic graphite (HOPG). The STM observation
was performed with no thermal drift corrections at room
temperature.
Results and Discussion
When we mixed a small amount of NMP solution of
PAn (0.05 wt %) into an aqueous solution of β-CD (1.8 wt
%) with the ratio of 1:24 and cooled the mixture with a
(7) French, D.; Levine, M.; Pazur, J.; Norberg, E. J. Am. Chem. Soc.
1949, 71, 353.
(8) Lewis, E. A.; Hansen, L. D. J. Chem. Soc., Perkin Trans. 2 1973,
2081.
(9) Anderson, S.; Aplin, R. T.; Claridge, T. D. W.; Goodson, T.; Maciel,
A. C.; Rumbles, G.; Ryan, J. F.; Anderson, H. L. J. Chem. Soc., Perkin
Trans. 1 1998, 2383.
(10) Ookubo, N.; Hirai, Y.; Ito, K.; Hayakawa, R. Macromolecules
1989, 22, 1359.
Langmuir, Vol. 15, No. 4, 1999 911
Figure 2. Typical experimental results of the FEB spectra in
the mixture solution of β-CD and PAn in NMP (a) at 255 K and
(b) at 300K.
refrigerator, blue precipitation appeared in the solution.
Such precipitation was not observed in an aqueous solution
of β-CD nor NMP solution of PAn with the same
concentration. Next we mixed R-CD and PAn similarly
and cooled the mixture solution. In this case, no precipi-
tation was observed in the solution. The appearance of
precipitation is considered as evidence of inclusion complex
formation between cyclic molecules and a polymer chain.11
Consequently, the present experimental results suggest
the inclusion complex formation between β-CD and
polyaniline.
Figure 2 shows typical experimental results of the FEB
spectra in the mixture solution of β-CD (4.4 × 10-3 M) and
PAn (2 × 10-3 wt %) in NMP (a) at 255 K and (b) at 300
K. In the solution, the number of β-CD molecules is 20
times more than that of monomer units of PAn. No FEB
signal is detected in the mixed solution at room temper-
ature as shown in Figure 2b. As temperature T decreases,
the FEB signal appears at 275 K and enlarges. In contrast,
NMP solutions of PAn alone show no FEB response even
at low temperatures down to 250 K.
As mentioned before, the FEB technique was applied
to another soluble conducting polymer, poly(3-hexyl-
thiophene), in solution in order to investigate the relation
between the main-chain conformation and the intramo-
lecular conduction mechanism.6 When the polymer con-
formation changed from rod to coil by the rod-coil
transition, the FEB signal becomes undetectable in the
coiled state. Thus, the present experimental results
indicate that PAn in NMP has coiled conformation at least
in the temperature range of 250-300 K, while PAn
together with β-CD in NMP changes into rodlike confor-
mation at low temperature below 275 K. This also suggests
the inclusion complex formation between β-CD and PAn
such as the molecular necklace.
From the rotational relaxation frequency (fr ) 3/(4πτr)),
at which K2ω′′ has a maximum, we can estimate the
effective length (Leff) of a rodlike molecule as12
9kBT
fr ) (ln(Leff/dr) + γr) (1)
2
2π η0 Leff3
(11) Harada, A.; Kamachi, M. Macromolecules 1990, 23, 2823.
(12) Nakajima, H.; Wada, Y. Biopolymers 1978, 17, 2291.
912 Langmuir, Vol. 15, No. 4, 1999 Letters

Figure 3. The temperature dependence of the effective length

Leff calculated from the rotational relaxation time τr with eq 1.
At temperature above 275 K, the FEB signal was not detected.

where η0 is the solvent viscosity, dr the diameter of the

rodlike molecule, γr a correction term for the end effect,
and kBT the thermal energy. The temperature dependence
of η0 was obtained from other experimental data.13-16 The
temperature dependence of Leff is shown in Figure 3, where
no FEB signal was observed at a temperature higher than
275 K. At a temperature below 275 K, Leff is almost
independent of temperature and is estimated to be about
1.5 µm. The tendency of Leff dropping off sharply with
increasing temperature is different from the rod-coil
transition of poly(3-hexylthiophene),17 where Leff changes
gradually from rod to coil. This would reflect the coopera-
tive effect of the inclusion complex formation. The value
1.5 µm of Leff is larger than the length 0.3 µm of PAn
evaluated from Mw. The rotational relaxation time in FEB
always gives us larger length than GPC because of the
polydispersity and the entanglement effect.6
Next, we observed the shape of the inclusion complex
between β-CD and PAn by STM, as shown in Figure 4a
and Figure 4b. The tip bias voltage was -500 mV and the
setting current was 0.30 nA. When a drop of the mixture
solution cooled at 255 K was spin-coated onto a substrate
of HOPG, almost all of the β-CD molecules and large
amount of the inclusion complexes were swept away from
the substrate since the surface of HOPG repels NMP
solution. But some complexes were caught by roughness
on the surface due to exfoliation of graphite layers as shown
in Figure 4a. Figure 4b exhibits the magnification of a
part of Figure 4a, where a rodlike structure with the length
of about 330 nm is seen clearly. This length agrees with
the contour length of PAn evaluated from Mw. As shown
in Figure 4c, the vertical height of this structure is about
2 nm, which is equal to the outside diameter of β-CD.
Incidentally, these rodlike structures were not observed
on the substrate where the solution of β-CD or PAn was
spin-coated.
As further evidence of the inclusion complex formation Figure 4. STM images where fields of view are (a) 1200 nm
between β-CD and PAn, we investigated the chemical × 1200 nm and (b) 350 nm × 350 nm. (c) The height profile of
oxidation or doping effect of PAn by iodine. It is known the cross section.
that iodine oxidizes PAn with emeraldine base18 and
changes the color of PAn solution from blue to violet. If mixture solution of β-CD (4.4 × 10-3 M) and PAn (2 × 10-3
PAn is completely covered by β-CD, it is expected that wt %) cooled at 255 K and kept the mixture at 273 K.
PAn should not be oxidized by iodine. We added 55 µL of Similarly, we prepared the mixture of PAn cooled at 255
a NMP solution of iodine (8 × 10-4 N) to 2 mL of the K and iodine without β-CD and kept it at 273 K. It was
found that the latter mixture changed the color from blue
(13) Ambrosone, L.; D’Errico, G.; Sartorio, R.; Vitagliano, V. J. Chem. to violet in a few days although the former still remained
Soc., Faraday Trans. 1995, 91, 1339. blue. At higher temperature, the former mixture including
(14) Chen, G.; Hou, Y.; Knapp, H. J. Chem. Eng. Data 1995, 40,
1005. β-CD also changed the color from blue to violet but a
(15) Garcia, B.; Alcalde, R.; Leal, J. M.; Matos, J. S. J. Phys. Chem. considerable delay of the change was observed in com-
B 1997, 101, 7991. parison to the latter mixture without β-CD. The detailed
(16) Guarino, G.; Ortona, O.; Sartorio, R.; Vitagliano, V. J. Chem.
Eng. Data 1985, 30, 366. results will be reported in a forthcoming paper.19 Con-
(17) Hotta, S., Ito, K. Electronic Properties of Polythiophenes, in
Handbook of Oligo- and Polythiophenes; Fichou, D., Eds; VCH: in press. (19) Yoshida, K.; Shimomura, T.; Ito, K.; Hayakawa, R., in prepara-
(18) Cao, Y. Synth. Met. 1990, 35, 319. tion.
Letters
sequently, it was confirmed that PAn was completely
covered by insulated CD molecules at low temperature.
This indicates that PAn forms the inclusion complex with
β-CD in NMP solution at low temperature as shown in
Figure 1c.
In conclusion, we observed the inclusion complex
formation between β-CD and PAn by FEB, STM, and the
doping effect. This inclusion complex, i.e., the insulated
molecular wire, is expected to have some unique features
(i) the conformation of PAn is confined to a rodlike
Langmuir, Vol. 15, No. 4, 1999 913
structure (all trans state) and hence the conjugated
structure can spread over the whole length of a conducting
polymer; (ii) PAn molecules are isolated from each other
by insulated CD molecules.
Acknowledgment. We thank Professor Toshio Nishi
for his support in the STM observation and Nitto Denko
Co. for supplying PAn.
LA9812471