Chemical Physics 238 Ž1998.

487–494

Volume phase transition of polymer gel in water and heavy water

Hideaki Shirota ) , Noriko Endo, Kazuyuki Horie
Department of Chemistry and Biotechnology, Graduate School of Engineering, UniÕersity of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo
113-8656, Japan

Received 10 August 1998

Abstract

We have investigated the deuterium isotope effect on the volume phase transition of a temperature-sensitive polymer gel
ŽpolyŽ N-isopropylacrylamide. gel.. The transition temperature of polyŽ N-isopropylacrylamide. gel in heavy water is about
18C higher than that in water. From the simulation based on a simple modified Flory–Rehner model, the deuterium isotope
effect on the volume phase transition of polyŽ N-isopropylacrylamide. gel is arising from the difference in the polymer–solvent
interactions in water and heavy water. q 1998 Elsevier Science B.V. All rights reserved.

1. Introduction The fundamental interactions for the volume phase

transition of polymer gels follow four molecular
Great attention has been paid to phase transitions
interactions: Ži. the van der Waals interaction, Žii.
and critical phenomena in polymer gels out of scien-
hydrophobic interaction, Žiii. electrostatic interaction,
tific interest and technological significance. The vol-
and Živ. hydrogen-bonding interaction. These interac-
ume phase transition of polymer gels was theoreti-
tions determine the phase behavior and molecular
cally predicted by Dusek and Patterson in 1968 w1x.
configuration. In the present study, we focus our
They showed the possibility of a discontinuous vol-
attention on the effect of hydrogen-bonding interac-
ume change of a polymer gel based on the analogy
tion on the volume phase transition, because hydro-
of the coil–globule transition of polymer chains in a
gen bonds play an important role in many chemical
solution. The volume phase transition was experi-
and biological systems.
mentally discovered for a partially ionized acryl-
One of the useful methods to investigate the
amide gel in a mixture of water and acetone by
hydrogen-bonding interaction is the isotopic ex-
Tanaka w2x. After that, the generality of a volume
change from hydrogen to deuterium of the hydroxyl
phase transition in polymer gels was recognized not
or amino hydrogen. Since the stabilization energy of
only by changing the composition of the solvent
w3–5x but also by temperature w6–9x, ionic and pH the hydrogen bond of deuterium is larger than that of
hydrogen arising from the difference in the zero-point
changes w10–12x, light irradiation w13,14x, electric
vibrational energies, both the static and dynamic
field w15,16x, and so on.
properties between normal and deuterated
hydrogen-bonding compounds are different from each
)
Corresponding author. other w17x. For example, the boiling and melting

0301-0104r98r$ - see front matter q 1998 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 1 - 0 1 0 4 Ž 9 8 . 0 0 3 4 0 - 1
488 H. Shirota et al.r Chemical Physics 238 (1998) 487–494
points of heavy water are higher than those of water
w18x. The dissociation energy of deuterated hydro-
gen-bonded complex Ž1-naphthol-d3 Žincluding OD
group. P ND 3 . was observed to be larger than that of
normal hydrogen-bonded complex Ž1-naphthol P
NH 3 . Žca. 120 cmy1 large dissociation energy for
deuterated complex. w19x. The higher unfolding tem-
peratures of some proteins in heavy water than in
water were also reported by several groups w20–22x.
In regard to the dynamic features, the deuterium
isotope effects of methanol ŽCH 3 OH, CH 3 OD,
CD 3 OH, and CD 3 OD. on the solvent relaxation were
clearly observed on both the hydroxyl and methyl
groups w23,24x. The extent of the isotope effect on
the hydroxyl group was larger than that on the
methyl group, and the two isotope effects were
additive in CD 3 OD. The Debye relaxation time of
heavy water was also larger than that of water Ž8.3
ps for water and 10.4 ps for heavy water. w25x. The
method of isotopic substitution is used for investigat-
ing not only the static and dynamic physical proper-
ties of hydrogen-bonded molecular systems but also
the mechanisms of chemical reactions such as elec-
tron transfer w26–30x.
As mentioned above, the isotopic substitution of
hydrogen of hydroxyl or amino groups is a very
useful method to investigate both the static and
dynamic properties of hydrogen-bonded systems. In
the present study we have investigated the deuterium
isotope effect on the volume phase transition of a
temperature-sensitive polymer gel, polyŽ N-isopro-
pylacrylamide. ŽPNIPA. gel. PNIPA gel in water is
one of the ideal systems for detailed studies of the
volume phase transition because this gel, with a
neutral network and with water, undergoes a nearly
critical phase transition as a function of temperature
around 348C w31–38x. Although the physical proper-
ties of water and heavy water are different and the
deuterium isotope effect is quite large in some cases,
some studies of the volume phase transition of poly-
mer gel Že.g. NMR, neutron scattering. ignore this
effect.
Our main focusing points are Ži. the difference in
transition temperatures between PNIPA gels in water
and heavy water and Žii. the origin of the deuterium
isotope effect on the volume phase transition of
PNIPA gel. In order to clarify the origin of the
deuterium isotope effect on the volume phase transi-
tion of PNIPA gel, the experimental results are
analyzed by the modified Flory–Rehner theory pro-
posed by Shibayama et al. w39x.
This paper is organized as follows. Experimental
methods are described in Section 2. Section 3 pre-
sents the experimental results of the deuterium iso-
tope effect on the volume phase transitions of PNIPA
gels. The modified Flory–Rehner model and the
parameters for simulation are discussed in Section 4.
The experimental results are discussed and compared
with the simulation results in Section 5. A brief
summary is presented in Section 6.
2. Experimental
PNIPA gels were prepared with a redox poly-
merization technique. N-Isopropylacrylamide ŽNIPA,
purchased from Tokyo Kasei. was purified by re-
crystallization from hexanerbenzene solution Ž2:1..
The concentrations of NIPA were 1000 and 300 mM.
The concentrations of the cross-linker, N, N X-methyl-
enebisacrylamide ŽBIS, Tokyo Kasei., were fixed at
12.53 and 3.76 mM by keeping the molar ratio of
NIPArBISs 79.8. The structures of the monomer
and cross-linker are shown in Fig. 1. The pregel
solution, containing NIPA, BIS, and 1.75 mM am-
monium persulfate Žinitiator. in distilled water, was
stirred for more than 15 min in an ice bath under
argon atmosphere. N, N, N X , N X-Tetramethylethylen-
ediamine Žaccelerator. was then added to be 8 mM.
After stirring for about 1 min, the solutions in mi-
cropipettes Ž1.20 mm in diameter, l 0 . were kept at
280 K for about 30 h. The cylindrical gels prepared
were taken out from the micropipettes and were
rinsed with water about 15 times for 7 days. N-De-
Fig. 1. The structures of the monomer and cross-linker used in the
present study.
 H. Shirota et al.r Chemical Physics 238 (1998) 487–494
uterated PNIPA gels ŽPNIPA-d gel. were prepared
from the normal PNIPA gels by isotopic substitu-
tions with D 2 O ŽIsotec, 99.9% D.. The isotopic
purity of the amino deuteriums of PNIPA-d gel was
estimated to be around 95% by 1 H-NMR measure-
ment.
The diameter of the gel, l, was measured as a
function of temperature with a microscope
ŽOLYMPUS, BX50.. The temperature of the gel in
water or heavy water was regulated with a thermo-
controller ŽLINKAM, LK600PM.. When the temper-
ature was changed, the diameter of the gel was
measured after reaching the thermal equilibrium Ž)
24 h near the phase transition region.. The measure-
ment of the gels were carried out from the low
temperature Ž228C. to the high temperature Ž508C..
3. Results
Fig. 2 shows the comparison of the temperature
dependence of the swelling ratio, lrl 0 , for PNIPA
Fig. 2. Temperature dependence of the swelling ratio, l r l 0 , for
PNIPA gel in water Žopen circles. and PNIPA-d gel in heavy
water Žclosed circles. with different initial monomer concentra-
tions ŽŽa. 300 and Žb. 1000 mM..
489
gels in water Žopen circles. and PNIPA-d gels in
heavy water Žclosed circles. with different initial
monomer concentrations, C0 ŽŽa. C0 s 300 mM and
Žb. C0 s 1000 mM.. The l is the diameter of a gel at
each temperature and l 0 is the initial diameter of a
gel Žthe inner diameter of a micropipette.. The transi-
tion temperatures of PNIPA gels in water are around
348C as are reported by several groups w31–38x.
The notable points from Fig. 2 are as follows. Ži.
The deuterium isotope effect on the volume phase
transition is clearly observed in both the higher and
lower C0 gels. Žii. The transition temperature of
PNIPA-d gel in heavy water is about 18C higher than
that of PNIPA-d gel in heavy water as was reported
by Shibayama et al. w31x. Žiii. In the swollen state,
lrl 0 of PNIPA-d gel in heavy water is larger than
that of PNIPA gel in water at each temperature.
These interesting results will be discussed and com-
pared with the simulation results based on the modi-
fied Flory–Rehner model proposed by Shibayama et
al. in Section 5.
4. Simulation of swelling–shrinking curve
Recently, Shibayama et al. reproduced the experi-
mental results on the temperature dependence of the
volume of PNIPA gel in water by a simple modified
Flory–Rehner model w38x. In this model, the effect of
the cross-linking arising from entanglements of a
polymer network is added to the original Flory–Re-
hner model. Especially, this model could reproduce
the swelling–shrinking curve of PNIPA gel in the
swollen state. We use the model to clarify the origin
of the deuterium isotope effect on the volume phase
transition in the present work. In this section we
briefly outline the theoretical framework of the model
and mention how to estimate the parameters.
4.1. Theoretical background
When a neutral polymer gel is in a swelling
equilibrium, the net osmotic pressure, P , becomes
zero. According to the original Flory–Rehner theory,
490 H. Shirota et al.r Chemical Physics 238 (1998) 487–494

P consists of two contributions: the mixing free This equation is used to semi-quantitatively discuss
energy and the elastic free energy w39–41x. the experimental results in the present study ŽSection
k BT 5, vide infra..
Psy f q ln Ž 1 y f . q xf 2
Vs 4.2. Simulation parameters of the swelling–shrinking
1 curÕe
1 f f 3
q n k BT
2 ž / ž /
f0
y
f0
Ž 1. In order to reproduce the swelling–shrinking
curves of PNIPA gels, the parameters in Eq. Ž5. are
where k B is the Boltzmann constant, T is the abso- determined in the following way w38x. f 0 is defined
lute temperature, Vs is the molar volume of the as,
solvent, n is the number of polymer chains between f 0 f VNIPA C0 Ž 6.
crosslinks per unit volume, x is Flory’s interaction where V NIPA is the molar volume of the NIPA
parameter, and f and f 0 are the network volume monomeric unit Ž0.103 lrmol. w43x. The n is fixed
fractions at swelling equilibrium and the reference to be the stoichiometric value.
states, respectively. In the right term of Eq. Ž1., the 2C BIS f 0
first term expresses the mixing free energy and the ns s 2C BIS Ž 7.
second term shows the elastic free energy. The x C0 V NIPA
parameter is assumed to be concentration dependent where C BIS is the concentration of the cross-linker
and can be expressed by w38,42x, ŽBIS.. Here, it is assumed that the molar volume of
x s x 1 q fx 2 Ž 2. BIS is as same as that of NIPA. Vs of water and
heavy water are 18.05 and 18.12 mlrmol, respec-
where
tively w44x. Although the densities of water and
D H y TD S heavy water are changeable at temperatures, the
x1 s Ž 3.
k BT swelling–shrinking curve is not largely affected by
and x 2 is a constant. D H and D S are the enthalpy the different values of the densities in the experimen-
and entropy per monomeric unit of the network tal range Ž22–508C.. The effect of the different
related to the volume phase transition. densities of water and heavy water at the different
In the modified Flory–Rehner model proposed by temperatures is, thus, neglected in the present study.
Shibayama et al., the number of polymer chains per The parameters determining x are chosen as the
unit volume, n , is replaced by w38x values reported by Hirotsu w45x. Namely, x 2 s 0.518,
C0 D H s y1.246 = 10y2 0 J, and D S s y4.717 =
n Ž 4. 10y2 3 JrK. However, these parameters were esti-
C0,ref mated for PNIPA gel in water. Actually, the deu-
where C0,ref is the lowest initial monomer concentra- terium isotope effect on the transition temperature
tion at which a uniform gel can be formed. Accord- Žand the swelling–shrinking curve. should be arising
ing to their experimental result, the lowest initial from the change in these parameters due to the
monomer concentration of NIPA is 300 mM. This isotopic substitutions. The values of x 2 , D H, and
relationship is reasonably assumed that the number D S for the PNIPA-d gel in heavy water will be
of effective cross-links can be proportional to the estimated by fittings and will be discussed in a later
initial monomer concentration. Thus Eq. Ž1. can be section.
rewritten as
1 Ž D H y TD S . f 2 5. Discussion
y f q ln Ž 1 y f . q q x2 f 3
Vs k BT
5.1. Deuterium isotope effect on the transition tem-
1 perature
C0 1 f f 3
qn
C0,ref 2 ž / ž /
f0
y
f0
s0 . Ž 5. Let us now consider the reason for the difference
between the temperature of the volume phase transi-
 H. Shirota et al.r Chemical Physics 238 (1998) 487–494 491

Table 1 perature of the volume phase transition of PNIPA-d

Physical properties of H 2 O and D 2 O at atmospheric pressure gel in heavy water thus becomes higher than that of
H 2O D2 O PNIPA gel in water.
Molecular weight Žgrmol. a 18.015 20.027 It is interesting to compare with the result of the
Melting temeperature Ž8C. a 0.00 3.82 phase separations of a cellulose in water and heavy
Boiling temperature Ž8C. a 100.00 101.42
water studied by Winnik w48x. She reported that the
Density Žgrcm3 . a,d 0.998 1.105
Dielectric constant b,d 80.18 79.76 lower critical solution temperature of cellulose in
Refractive index a,d 1.33283 1.33844 heavy water was 0.58C lower than that in water, and
Viscosity ŽmPaPs. e 0.890 a 1.095 c concluded that the lower critical temperature of a
a cellulose in heavy water is arising from the stronger
Ref. w44x.
b
Ref. w46x.
hydrophobic interaction of the polymer in heavy
c
Ref. w47x. water than in water. The result seems to be the
d
Values at 208C. opposite feature of the deuterium isotope effect in
e
Values at 258C. contrast to the present result. The difference in the
deuterium isotope effect might be due to the differ-
ence in the interactions between polymer and solvent
tion of PNIPA-d gel in heavy water and that of Žnamely, strongly hydrated polymer and entropically
PNIPA gel in water. In the swollen state, the poly- stabilized polymer.. Such different features of the
mer network is hydrated by water molecules. In deuterium isotope effects on the coil–globule transi-
other words, the polymer Žmainly functional group. tion of linear polymers and the volume phase transi-
strongly interacts with water molecules through in- tion of polymer gels for the change in solvent com-
termolecular hydrogen bonds. In contrast to the position are also observed w49x.
swollen state, the polymer chains hydrophobically
interact with each other in the shrunken state. The 5.2. Comparison with the simulation result
volume phase transition temperature is determined
by the balance between both the states Žnamely, Fig. 3 shows the comparison of the swelling–
interaction strength.. shrinking curve of PNIPA gel in water predicted by
The difference in the static physical properties of the modified Flory–Rehner theory Ž C0 s 300 mM:
water and heavy water may give us some important solid line and C0 s 1000 mM: broken line. and
information. Table 1 is summarized some static obtained by experiment Ž C0 s 300 mM: circles and
properties of water and heavy water w18,44,46,47x. C0 s 1000 mM: squares.. It is clear from the simula-
As well-known, both the melting and boiling points tion result that the low initial concentration gel
of heavy water are higher than those of water. The
viscosity of heavy water is also higher than that of
water. These phenomena are explained by the cate-
gory of the hydrogen-bonding interactions. The
zero-point vibrational energy of intermolecular hy-
drogen bond in heavy water becomes lower due to
the heavier mass. The higher dissociation energy of
deuterated hydrogen-bonded complex in gas phase
was observed by Burgi¨ et al. w19x. By analogy, more
stabilized hydrogen-bonding structure in heavy water
can be expected than in water. In the case of the
present result, the stabilization of the hydrogen-bond-
ing interaction between the amide groups of PNIPA Fig. 3. Comparison of the swelling–shrinking curves of PNIPA
gel with different initial monomer concentrations Ž C0 . obtained by
gel and water molecules becomes larger by the iso- the experiment Žcircles for C0 s 300 mM and squares for C0 s
topic exchanges of the source of the hydrogen bonds 1000 mM. and predicted by the modified Flory–Rehner theory
Žhydroxyl hydrogen and amide hydrogen.. The tem- Žsolid line for C0 s 300 mM and broken line for C0 s1000 mM.
492 H. Shirota et al.r Chemical Physics 238 (1998) 487–494
Ž C0 s 300 mM. shows the discontinuous feature at
around 358C, and the high initial concentration gel
Ž C0 s 1000 mM. shows the continuous feature. This
tendency of the simulation result is very similar to
the experimental result. It is also clear from the
figure that the curves are well-fitted in the swollen
state by the theory. The deuterium isotope effect on
the swelling–shrinking curve of PNIPA gel should
be focused on the swollen state and the transition
point, and the simulation parameters should be based
on those of PNIPA gel in water.
Since the hydrogen-bonding interactions of hydro-
gen and deuterium are different, the changeable pa-
rameters by isotopic substitutions are x 2 , D S, and
D H consisting x ŽEqs. Ž2. and Ž3... Let us consider
these parameters independently. Fig. 4 shows the
effect of x 2 on the swelling–shrinking curve of
PNIPA gel ŽŽa. C0 s 300 mM and Žb. C0 s 1000
Fig. 4. Deuterium isotope effect of x 2 on the swelling–shrinking
curves of PNIPA gel with different initial monomer concentra-
tions ŽŽa. 300 and Žb. 1000 mM. obtained by the modified
Flory–Rehner theory. PNIPA gel in water is shown by solid line
Ž x 2 s 0.518 estimated by Hirotsu w45x. and PNIPA-d gel in heavy
water is shown by broken line Ž x 2 s 0.445.. Experimental results
are also shown by symbols Žopen circles for PNIPA gel in water
and closed circles for PNIPA-d gel in heavy water..
mM.. The experimental data are given by symbols
Žopen circles, undeuterated; closed circles, deuter-
ated. and the simulated results are shown by lines
Žsolid, undeuterated; broken, deuterated.. In order to
examine the deuterium isotope effect of x 2 on the
swelling–shrinking curve of PNIPA-d gel in heavy
water, the same values as for PNIPA gel in water
w45x are used concerning the other parameters Ž D S
and D H . for PNIPA-d gel in heavy water. The value
of x 2 for PNIPA-d gel in heavy water are tenta-
tively determined by the best fitting of the critical
temperature. For the fitting of the swelling–shrink-
ing curve of PNIPA-d gel in heavy water, the value
of x 2 is put at 0.445. It is clear from the figure that
the deuterium isotope effect in the swollen state
experimentally obtained cannot be reproduced by the
theory. Namely, although the experimentally ob-
tained lrl 0 of the PNIPA-d gel in heavy water is
larger in the swollen state than that of PNIPA gel in
water, the result obtained by the simulation shows
the slightly opposite feature. We thus conclude that
the deuterium isotope effect on the swelling–shrink-
ing curve of PNIPA gel in water is not arising from
the effect of x 2 .
The effect of D S on the swelling–shrinking curve
is shown in Fig. 5 ŽŽa. C0 s 300 mM and Žb. C0 s
1000 mM.. The experimental results are shown by
open circles for PNIPA gel in water and closed
circles for PNIPA-d gel in heavy water, and the
theoretical results are shown by a solid line for
PNIPA gel in water and a broken line for PNIPA-d
gel in heavy water. The value of D S for PNIPA-d
gel in heavy water is obtained to be y4.699 = 10y2 3
JrK by the best fitting of the critical temperature
without changing x 2 and D H w45x. It is clear from
the result of the simulation that the lrl 0 in the
swollen state of PNIPA gel in water and of PNIPA-d
gel in heavy water are exactly same. Thus the change
of D S cannot reproduce the deuterium isotope effect
of the swelling–shrinking curve of PNIPA-d gel in
heavy water obtained experimentally.
Fig. 6 shows that the effect of D H of the
swelling–shrinking curve Žopen circles, experimental
PNIPA gel in water; closed circles, experimental
PNIPA-d gel in heavy water; solid line, simulated
PNIPA gel in water and simulated PNIPA-d gel in
heavy water. of the low initial concentration Ž C0 s
300 mM. PNIPA gel Ža. and the high initial concen-
 H. Shirota et al.r Chemical Physics 238 (1998) 487–494 493

tration Ž C0 s 1000 mM. PNIPA gel Žb.. Here, the

value of D H for PNIPA-d gel in heavy water is
estimated to be y1.252 = 10y2 0 J by the best fitting
of the critical temperature of PNIPA-d gel in heavy
water without changing x 2 and D S. It is clear from
the figure that the feature of the deuterium isotope
effect on the swollen state and the volume phase
transition obtained experimentally is semi-quantita-
tively reproduced. The value of D H of PNIPA-d gel
in heavy water is more negative than that of PNIPA
gel in water. This is quite reasonable because the
hydrogen-bonding interaction becomes stronger by
the isotopic substitutions. In other words, the hydro-
gen-bonding network in deuterium is more stabilized
than that in hydrogen. Although all three parameters
are changeable, the present simulation results suggest
that the deuterium isotope effects on the swelling–

Fig. 6. Deuterium isotope effect of D H on the swelling–shrinking

curves of PNIPA gel with different initial monomer concentra-
tions ŽŽa. 300 and Žb. 1000 mM. obtained by the modified
Flory–Rehner theory. PNIPA gel in water is shown by solid line
Ž D H sy1.246=10y2 0 J estimated by Hirotsu w45x. and PNIPA-d
gel in heavy water is shown by broken line Ž D H sy1.252=
10y2 0 J.. Experimental results are also shown by symbols Žopen
circles for PNIPA gel in water and closed circles for PNIPA-d gel
in heavy water..

shrinking curve and the critical temperature of PNIPA

gel should be mainly arising from the different D H
between hydrogen and deuterium.

6. Conclusion

We have investigated the deuterium isotope effect

Fig. 5. Deuterium isotope effect of D S on the swelling–shrinking
curves of PNIPA gel with different initial monomer concentra-
tions ŽŽa. 300 and Žb. 1000 mM. obtained by the modified
Flory–Rehner theory. PNIPA gel in water is shown by solid line
Ž D Ssy4.717=10y2 3 JrK estimated by Hirotsu w45x. and
PNIPA-d gel in heavy water is shown by broken line Ž D Ss
y4.699=10y2 3 JrK.. Experimental results are also shown by
symbols Žopen circles for PNIPA gel in water and closed circles
for PNIPA-d gel in heavy water..
on the volume phase transition of PNIPA gel. The
transition temperature of PNIPA-d gel in heavy wa-
ter is about 18C higher than that of PNIPA gel in
water. The swelling–shrinking curves of PNIPA gels
in water and PNIPA-d gels in heavy water are
semi-quantitatively reproduced by the simulations
based on a simple modified Flory–Rehner model.
The deuterium isotope effect on the swelling–shrink-
ing curve should be mainly arising from the different
494 H. Shirota et al.r Chemical Physics 238 (1998) 487–494
D H of the polymer networks in water and heavy
water.
Acknowledgements
We are grateful to Prof. Mitsuhiro Shibayama,
Kyoto Institute of Technology, for his helpful discus-
sion. We are also grateful to Mr. Tokiji Kawamura,
University of Tokyo, for his kind help in 1 H-NMR
measurement. This work is supported in part by a
Grant-in-Aid for Scientific Research ŽNo. 08405060.
from Ministry of Education, Science, Sports and
Culture of Japan.
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