J. Phys. Chem.

B 2000, 104, 7077-7081 7077

Osmotic Coefficient of a Synthetic Rodlike Polyelectrolyte in Salt-Free Solution as a Test of

the Poisson-Boltzmann Cell Model

J. Blaul, M. Wittemann, and M. Ballauff*

Polymer-Institut, UniVersität Karlsruhe, Kaiserstrasse 12, 76128 Karlsruhe, Germany

M. Rehahn
Institut für Makromolekulare Chemie, Technische UniVersität Darmstadt, Petersenstrasse 22,
D-64287 Darmstadt, Germany
ReceiVed: April 13, 2000

A comparison of the osmotic coefficient of a synthetic stiff-chain polyelectrolyte with the prediction of the
Poisson-Boltzmann (PB) cell model is presented. The polyelectrolyte consists of a poly(p-phenylene) backbone
with attached cationic groups (charge parameter 3.4) and either chloride or iodine counterions. The osmotic
coefficient φ was deduced from the osmotic pressure measured from dilute solutions (0.05-3.6 g/L) without
added salt. The data demonstrate that the PB cell model captures the essential features of the experimental
results without adjustable parameters. It fails to give a quantitative description, however, because the
experimental φ is significantly smaller than the value predicted by the PB cell model. Possible reasons for
this discrepancy as the neglect of the ion-ion correlations or specific interactions between the macroion and
the counterions in the PB cell model are discussed.

Introduction with λB being defined through

Polyelectrolytes consist of long linear polymer chains with

attached groups that dissociate in polar solvents into a macroion
and counterions of opposite charge.1-4 The strong electric field
leads to a distinct spatial correlation of the counterions with
the macroion which vastly exceeds the correlation of dissolved
ions in low-molecular-weight systems. This correlation of the
counterions and the macroion becomes directly evident when
considering the osmotic pressure Π of polyelectrolytes in dilute
solution. The effect of the marked reduction of the activity of
counterions with the macroion can be expressed through the
osmotic coefficient φ defined by
Π solution must be used.1 The cell model has frequently been used
φ) (1)
Πid
where Πid is the ideal osmotic pressure calculated for a solution
of free counterions.1-4 It has been known for a long time that
the osmotic coefficient of polyelectrolytes is considerably
smaller than unity.5,6 The first quantitative explanation of this
effect was given by Fuoss, Katchalsky, and Lifson7 and
independently by Alfrey, Berg, and Morawetz8 by applying the
Poisson-Boltzmann (PB) cell model4,9 to the problem of a
cylindrical macroion. In the frame of PB theory, the rodlike
polyelectrolyte is characterized by the charge parameter ξ which
is defined through the ratio of the Bjerrum length λB to the
contour distance per unit charge b:
λB
ξ) (2)
b compared to experimental data in a quantitative manner. They
* Corrsponding author. E-mail: Matthias.Ballauff@chemie.uni-
karlsruhe.de.
10.1021/jp001468r CCC: $19.00 © 2000 American Chemical Society
Published on Web 07/07/2000
e2
λB ) (3)
4π0kBT
where e is unit charge,  is the dielectric constant of the medium,
and e0, kB, and T have their usual meanings.1-4 The rodlike
macroions are assumed to have infinite length. Furthermore,
they are confined in a periodic array of parallel cylindrical
Wigner-Seitz cells which greatly facilitates the solution of the
PB equation. For salt-free solutions, the cell model provides an
analytical expression for the distribution of the counterions
around the macroion;7,8 in the case of added salt, a numerical
in comparisons with experimental data since it allows to
calculate the osmotic coefficient3,7,10 as well as the partial
scattering function of rodlike polyelectrolytes as measured by
small-angle neutron scattering.11-13
Moreover, an important conclusion to be drawn from the cell
model is the fact that even at highest dilution a fraction of the
counterions cannot be diluted away if the charge parameter ξ
exceeds unity.1-3 For infinitely long macroions with ξ > 1, the
electrostatic attraction wins over the entropy of dilution and a
given fraction is condensed onto the macroion. The concept of
counterion condensation2 was later fully exploited by
Manning14-17 who derived his well-known limiting laws for
linear polyelectrolytes. It must be kept in mind, however, that
these limiting laws only apply at exceedingly low concentrations
which cannot be attained by experiments.3,17 Hence, the
quantitative conclusions drawn from these laws cannot be
are, however, an excellent qualitative guideline and allow to
treat macroions with multivalent counterions in solutions
containing added salt.
7078 J. Phys. Chem. B, Vol. 104, No. 30, 2000
The problem of counterion condensation has recently been
elucidated by Deserno, Holm, and May18 who compared the
predictions of the PB cell model to computer simulations. These
authors could also discuss the shortcomings of the PB cell model
which as a mean-field approach neglects the correlations of the
counterions. In the case of monovalent counterions, the latter
effect leads only to small corrections. The PB model arrives at
qualitatively wrong conclusions, however, if the counterions are
divalent or multivalent. In this case, pronounced overcharging
effects are seen which do not appear on the mean-field level.
This finding is in full accord with the results of the modified
Poisson-Boltzmann theory (MPB) propounded by Outhwaite
and co-workers.19-20
Recently, the PB cell model has come under attack by
Nyquist, Ha, and Liu who called attention onto the various
unrealistic assumptions of this theory.21 In particular, these
authors stated correctly that a solution of rods of finite length
should not exhibit counterion condensation in the limit of zero
concentration. Their theory predicts an osmotic coefficient which
approaches unity in the limit of low concentration. In addition
to this, Kuhn, Levin, and Barbosa22 raised general doubt on the
validity of the Wigner-Seitz picture as applied to an isotropic
solution of rodlike molecules. Their theory can be applied to
systems at finite concentration and predicts a smoothing out of
the sharp counterion condensation predicted by the Manning
model.14-17 It therefore becomes apparent that there is no
generally accepted theoretical description of solutions of rodlike
macroions yet despite decades of research.
Up to now the osmotic coefficient has repeatedly been
measured for a great variety of synthetic and natural
polyelectrolytes.1-3,5,6,23-29 Most of the systems studied so far
consist of flexible polyelectrolytes dissolved in water. The
application of the PB cell model to flexible polyelectrolytes,
however, is less straightforward because these macroions do
not assume a fully stretched conformation in solution.30 Careful
measurements24-27 of the osmotic coefficient of aqueous salt-
free solutions of poly(styrenesulfonate) demonstrated that the
PB cell model accounts for the experimental data only in a
satisfactory way if the charge parameter ξ is treated as an
adjustable parameter. Hence, poly(styrenesulfonic acid) requires
an adjusted value of ξ which is approximately 1.4 times larger
than the structural value.1,27 The reasons for this marked
discrepancy are not yet clear.1,27 In the case of flexible
polyelectrolytes, there is an intricate relation between the
conformation of the macroion and the spatial distribution of
the counterions and these systems cannot be used to test the
validity of the cell model.
From its derivation it is obvious that the cell model holds
true in a strict sense only if the macroion assumes a rodlike
shape. DNA in salt-free solution can be regarded as such a
model polyelectrolyte and early measurements by Auer and
Alexandrowicz23 showed that for solutions of DNA φ is located
indeed in the range predicted by theory. The stability of the
helical conformation, however, is severely impeded if the ionic
strength is low. The measurements of Auer and Alexandrowicz
had therefore to be done at low temperature to avoid the melting
of the helix. Hence, rodlike helical polymer are therefore of
limited use for a comprehensive study of the osmotic coefficient.
From this brief survey it is obvious that the problem of the
osmotic coefficient of flexible polyelectrolytes is far from being
resolved. A systematic study of φ obtained from a synthetic
stiff-chain polyelectrolyte for which the conformation is inde-
pendent of the ionic strength would help to clarify this problem.
In a recent publication,31 we introduced a cationic polyelectrolyte
Blaul et al.
SCHEME 1
based on the poly(p-phenylene) (PPP) backbone. Because of
the high persistence length of the symmetrically substituted PPP
structure which is of the order of 20 nm,32 these polyelectrolytes
present highly suitable model compounds for nearly rodlike
macroions. In principle, the application of the PB cell model
should be possible without adjustable parameters for these
systems. This is due to the fact that the charge parameter is
fixed by the chemical structure of the rodlike macroions.
Moreover, the diameter of the macroions in solution can be
determined independently by small-angle X-ray scattering33
(SAXS). Their excellent stability makes them good candidates
for the study of solution properties throughout a wide range of
concentrations and temperatures.
Here we present the first study of the osmotic coefficient φ
measured in salt-free solution of the PPP polyelectrolyte 1
(Scheme 1). Measurements of 1 with different counterions (Cl-,
I-) give additional information on possible specific interactions
of the macroion with the counterions.
The structural value of the charge parameter ξ of this system
is given by 3.4 and the persistence length of the main chain
(20 nm, ref 32) is high enough to regard these polymers as
rodlike. Thus, for typical degrees of polymerization (ca. 40-
60), one macromolecules comprises approximately one persis-
tence length. First studies of 1 by SAXS33 as well as measure-
ments of electrical birefringence in dilute solution34 demonstrated
that 1 dissolves in water in a molecularly disperse fashion. It is
necessary for the present purpose that the polyelectrolyte
molecules fully dissolve to yield meaningful data of φ, of course.
This is in contrast to PPP polyelectrolytes of different molecular
architecture which may associate in aqueous solution to form
well-defined micellar aggregates.35 For the present system 1,
however, formation of micelles can be ruled out clearly.33,34
Theory
We consider a system of rodlike macroions dissolved in water
without added salt. In this case the PB cell model can be solved
exactly7,8,36 to yield the osmotic coefficient for finite concentra-
tions of the polyelectrolyte. As input parameters the cell model
requires the charge parameter ξ (eq 2) which is fixed by the
chemical structure of the rodlike macroion. For the system under
consideration here (cf. Scheme 1) ξ ) 3.4 (length of the
repeating unit, 0.43 nm; b ) 0.215 nm; λB ) 0.73 nm in water
at 40 °C). The length L of the macroions is calculated from the
number-average molecular weight31 of polyelectrolyte 1 used
here (number-average degree of polymerization ) 40; see
below). The other parameter necessary for the calculation of φ
is the minimum distance of contact of the macroion and the
counterions termed a.7,8,36 This parameter is taken from a
previous analysis of the polyelectrolyte 1 by small-angle X-ray
scattering (SAXS) which gave a ) 0.7 nm.33
With these parameters being fixed, the calculation of φ
proceeds as follows:7,36 The cell radius R follows from the
Osmotic Coefficient of a Synthetic Rodlike Polyelectrolyte
condition that (N/V)πLR2 ) 1. The osmotic coefficient may be
obtained from7
1 - β2
φ) (4)
2ξ
Here β is an integration constant which follows from the
numerical solution of the equation36
arctan (ξ -β 1) + arctan(β1) + β ln(Ra) ) 0 (5)
For the salt-free solutions, the Manning theory arrives for ξ >
1 at a particularly simple result for the osmotic coefficient at
infinite dilution, namely
1 (b) polyelectrolyt 1 with iodine counterions; (3) 1 with chloride
φ) (6)
2ξ
It may be shown that eq 6 is the limit of eq 4 for N/V f 0.3 As
already stated above, however, this limit is only attained for
concentration of the polyelectrolyte so low that they cannot be
reached experimentally. This is due to the fact that the
concentration of the polyelectrolyte enters only through the
factor ln(a/R) in eq 5.
Experimental Section
The polyelectrolyte 1 was prepared and characterized as
described recently.31 The number-average degree of polymer-
ization Pn as determined from the uncharged precursor was 40.
The degree of substitution was higher than 99% as determined
by NMR spectroscopy.
Dilute solutions of 1 were prepared in water purified by
reverse osmosis and ion exchange (Millipore Milli-Qplus). In
the course of this study, it turned out that even the smallest
amounts of oligomeric impurities will give spurious signals in
the measurements of the osmotic pressure. These impurities were
removed by prolonged ultrafiltration. In a typical run, 350 mL
of the polyelectrolyte solution having a concentration of ca. 1
g/L was placed in an ultrafiltration cell equipped with a filter
made from regenerated cellulose (Millipore; pore size 30.000
nominal molecular weight limit). Serum replacement was
achieved by a flow of ca. 10 L of pure water with an pressure
of 1.5 bar. Attempts to use dialysis as a means of purification
failed to give satisfactory results.
The osmotic pressure was determined at 40 °C using a
Gonotec Osmomat 090 equipped with a Sartorius cellulose
triacetate membrane (nominal molecular weight cutoff 5000).
The slightly elevated temperature had been chosen to ensure
better thermostating. For carefully purified solutions the osmotic
pressure was found to be constant over at least 10 min after
injection. In the presence of small amounts of impurities, the
osmotic pressure first attains a maximal value after injection
but decreases subsequently to reach a lower plateau. In this case,
a negative read-out of the osmometer resulted after injection of
pure water in the cell. For clean solutions, however, no effect
resulted after replacing the polymer solution by water again.
From synthesis,31 iodine counterions result which may be
exchanged by chloride ions through serum replacement by using
a 0.02 M solution of KCl. Afterwards, the KCl solution is
replaced by pure water and the above cleansing procedure is
repeated.
Results and Discussion
The present experimental study confirms older observations24
that small amounts of impurities may severely affect the
J. Phys. Chem. B, Vol. 104, No. 30, 2000 7079
Figure 1. Osmotic coefficient φ (see eq 1) of polyelectrolyte 1 in
aqueous solution as a function of the concentration cc of counterions:
counterions. The solid line marks the theoretical value of φ calculated
by use of the PB-cell model (eqs 4 and 5). For this calculation the
charge parameter ξ ) 3.4 derived from structural data has been used.
The long-dashed line gives the Manning limit (eq 6) whereas the short-
dashed line shows the best description of data within the PB model
using ξ as an adjustable parameter (ξ ) 3.8). See text for further
explanations.
accuracy of the measured osmotic coefficient. Only if the
solution of the polyelectrolyte was subjected to exhaustive serum
replacement through ultrafiltration could the osmotic pressure
be measured in a reproducible manner. The spurious effects seen
in osmotic measurements before purification are most probably
due to small amounts of oligomeric material which still can
permeate the membrane.
Figure 1 displays the osmotic coefficient φ measured for
solutions of 1 with chloride counterions (triangles) and with
iodine counterions (filled circles). It is directly obvious that φ
remains practically constant throughout the range of concentra-
tion employed here; there is no upturn at the lowest concentra-
tions. This is in full accord with all previous experimental
findings1,23-29 which clearly demonstrated that φ is virtually a
constant at small concentrations. It is not in accord with ref 21,
however, which predicts an upturn at similar concentrations.
The data furthermore show that there is a difference between φ
measured for I- counterions as opposed to Cl- counterions. This
is in contrast to the PB cell model and directly points to specific
interactions of the counterions with the macroion which are not
included in theory.1,17, 27
The solid line in Figure 1 was calculated using the charge
parameter ξ following from the molecular structure of poly-
electrolyte 1, namely ξ ) 3.4. Model calculations showed that
the second input parameter a, the minimum distance at the
contact of macroion and counterions has a small influence only.
Alterations of a by 20% shift the calculated osmotic coefficient
by ca. 5% which is within the limits of experimental error. This
is evident from eq 5 where only ln(a/R) enters into the
determination of β. On the other hand, the charge parameter ξ
has a profound influence on φ.
In this context, it is interesting to note that the scattering
intensity measured by SAXS is highly sensitive toward the
minimum distance a at contact of macroion and counterions
and allows to determine this parameter with excellent accuracy.33
Calculations in the frame of the PB cell theory furthermore show
that the charge parameter ξ is less influential when modeling
the SAXS data. On the other hand, the osmotic coefficient φ
measured here is highly sensitive toward ξ and less sensitive
toward a. In this respect, the present investigation of φ and
scattering experiments33 supplement each other in a virtually
ideal fashion.
7080 J. Phys. Chem. B, Vol. 104, No. 30, 2000
Figure 2. Osmotic coefficient φ (see eq 1) of DNA in aqueous solution
as a function of the concentration cc of counterions at 5 °C. The data
have been taken from the work of Auer and Alexandrowicz.23 The solid
line marks the theoretical value of φ calculated by use of the PB cell
model (eqs 4 and 5). For this calculation the charge parameter ξ )
4.12 derived from structural data has been used. The dashed line shows
the best description of data within the PB model using ξ as an adjustable
parameter (ξ ) 4.60). See text for further explanations.
Since φ does not depend strongly on the molecular input
parameter a, the comparison of the experimental osmotic
coefficient with the prediction of the PB cell model proceeds
virtually without adjustable parameter. Figure 1 demonstrates
clearly that the PB theory overestimates the osmotic coefficient
φ considerably, in particular in the case of Cl- counterions.
Neutron diffraction data obtained by Bieze et al.37 suggest that
a cationic polyelectrolyte may seriously affect the hydration shell
of chloride ions which leads to a close contact between macroion
and counterion. This would explain the reduced activity of the
Cl- ions as opposed to the I- ions seen in the present system.
Further experiments are desirable to elucidate this point further.
No such effects are expected in the case of the I- ions and in
the following the comparison of theory and experiment is
restricted to the osmotic coefficient φ measured for polyelec-
trolyte 1 in the presence of I- (circles in Figure 1).
The osmotic coefficient of 1 in the presence of I- counterions
is located between the prediction of the cell model (solid line
in Figure 1) and the Manning limit as calculated by eq 6 (long-
dashed line in Figure 1). Only if ξ is raised to 3.8 a
semiquantitative description of the experimental data is obtained.
The short-dashed line in Figure 1 displays the respective
calculation using ξ ) 3.8 which provides a sufficient fit, at least
in the regime of lower polyelectrolyte concentrations. It is
interesting that the data of Auer and Alexandrowicz23 lead to
the same conclusion: Figure 2 displays a comparison of their
data with the PB cell model. The osmotic coefficient obtained
by these authors from aqueous salt-free solutions of DNA at 5
°C are much better described if the structural charge parameter
ξ ) 4.12 (solid line in Figure 2) is replaced by a considerably
higher value of ξ ) 4.60 (dashed line in Figure 2).
This is in accord with previous findings24-27 obtained from
flexible polyelectrolytes. Here too, the measured value of φ was
found to be lower than the values calculated from the PB cell
model with the use of the correct charge parameter ξ. In the
case of flexible polyelectrolytes this could be rationalized by
assuming an “effective charge parameter” which is higher than
the value obtained from structural data and adjusted to match
the experimental data.1 The reason for a higher effective ξ was
sought in the locally curved conformation of the flexible main
chain. The counterions then “see” an effective main chain being
higher charged than the fully stretched chain. Hence, their
activity is lowered concomitantly. Obviously, this explanation
is ruled out totally for the rodlike polyelectrolyte 1 under
Blaul et al.
investigation here as well as for DNA studied by Auer and
Alexandrowicz.23 Obviously, other explanations need to be
sought.
One reason for the discrepancy of the PB cell model and the
experimental data seen in Figure 1 may be due to the fact that
the PB model is a mean-field approach. This point is well-known
and has been discussed by a number of authors recently (see
refs 18-20 and further citations given there). The charge
fluctuations neglected in the mean-field PB model may even
lead to counterion-mediated attraction between the rodlike
macroions if divalent counterions are present.38 While the effects
of ion correlations are most pronounced in the case of divalent
and multivalent counterions, they may also lead to small but
significant differences in the case of monovalent counterions
at higher densities. Recently, this problem has been discussed
in detail by Das et al.19 These authors showed by simulations
as well as by calculations in the frame of the modified Poisson-
Boltzmann theory that the concentration at the cell boundary
determining φ is lowered by 7-13% when considering the ion
correlations properly. The discrepancies between theory and
experiment seen in the present investigation exceed this differ-
ence and additional factors influencing φ must be identified:
(i) One possible reason for the observed discrepancy of theory
and experiment may be sought in a locally varying dielectric
constant. The immediate neighborhood of the macroion may
exhibit a considerably lower dielectric constant than the bulk
water.42 This must necessarily lead to a stronger interaction of
the macroion with the counterions as observed in the present
investigation.
(ii) The present comparison of φ measured in the presence
of Cl- and I- counterions points to additional specific interac-
tions between the macroion and the counterions. Such specific
interactions are known since a long time (see ref 1 and further
references given there) and have been repeatedly treated in the
literature.2,3,17,27,39-41 A possible explanation for the reduced
activity of the I- ions may be sought in the van der Waals
attraction of the macroion and the polarizable counterions.
Additional experiments using bulkier and less polarizable
counterions will elucidate this point further.
Conclusions
An investigation of the osmotic coefficient φ of salt-free
aqueous solutions of a synthetic rodlike polyelectrolyte has been
presented. To the authors’ best knowledge, this is the only study
of φ of a rodlike polyelectrolyte in salt-free solution since the
work of Auer and Alexandrowicz in 1969. It has been shown
that φ as a function of polyelectrolyte concentration presents a
critical test for the PB cell model of rodlike polyelectrolytes.
The measured data of φ cannot be described quantitatively by
the PB theory. A semiquantitative fit of φ can only be achieved
by raising the charge parameter ξ. The small but significant
discrepancy of the PB theory and the experimental values may
be traced back to the deficiency of the cell model, namely the
neglect of ion-ion correlations,18-20 and specific inter-
actions27,39-41 between the macroion and the counterions not
included in theory. A locally varying dielectric constant would
lead to the same effect.42 It is nevertheless evident that the cell
model gives a semiquantitative estimate of φ despite its
simplicity.
Acknowledgment. The authors are indebted to Markus
Deserno und Christian Holm for many fruitful discussions.
Financial support by the Deutsche Forschungsgemeinschaft,
Schwerpunkt Polyelektrolyte, is gratefully acknowledged.
Osmotic Coefficient of a Synthetic Rodlike Polyelectrolyte
References and Notes
(1) Mandel, M. Polyelectrolytes; In Encyclopedia of Polymer Science
and Engineering, 2nd ed.; Mark, F. H., Bikales, N. M., Overberger, C. G.,
Menges, G., Eds.; Wiley: New York, 1988; Vol. 11, p 739.
(2) Oosawa, F. Polyelectrolytes; Marcel Dekker: New York, 1971.
(3) Katchalsky, A. Pure Appl. Chem. 1971, 26, 327.
(4) Schmitz, K. S. Macroions in solution and in colloidal suspension;
VCH Publishers: New York, 1993.
(5) Kern, W. Z. Phys. Chem. 1938, A181, 268.
(6) Kern, W. Z. Phys. Chem. 1939, A184, 197.
(7) Fuoss, R. M.; Katchalsky, A.; Lifson, S. Proc. Natl. Acad. Sci.
U.S.A. 1951, 37, 579.
(8) Alfrey, T.; Berg, P. W.; Morawetz, H. J. Polym. Sci. 1951, 7, 543.
(9) Mandel, M. J. Phys. Chem. 1992, 96, 3934.
(10) Marcus, R. A. J. Chem. Phys. 1955, 23, 1057.
(11) van der Maarel, J. R. C.; Groot, L. C. A.; Mandel, M.; Jesse, W.;
Jannink, G.; Rodriguez, V. J. Phys. II Fr. 1992, 2, 109.
(12) Kassapidou, K.; Jesse, W.; Kuil, M. E.; Lapp, A.; Egelhaaf, S.;
van der Maarel, J. R. C. Macromolecules 1997, 30, 2671.
(13) van der Maarel, J. R. C.; Kassapidou, K. Macromolecules 1998,
31, 5734.
(14) Manning, G. S. J. Chem. Phys. 1969, 51, 924, 934, 3249.
(15) Manning, G. S. Ann. ReV. Phys. Chem. 1972, 23, 117.
(16) Manning, G. S. In Polyelectrolytes; Sélegny, E., Mandel, M.,
Strauss, U. P., Eds.; Reidel: Dordrecht, 1974; p 9.
(17) Manning, G. S. J. Phys. Chem. 1984, 88, 6654.
(18) Deserno, M.; Holm, Ch.; May, S. Macromolecules 2000, 33, 199.
(19) Das, T.; Bratko, D.; Bhuiyan, L. B.; Outhwaite, C. W. J. Phys.
Chem. 1995, 99, 410, and further literature cited there.
(20) Das, T.; Bratko, D.; Bhuiyan, L. B.; Outhwaite, C. W. J. Chem.
Phys. 1997, 107, 9197.
(21) Nyquist, R. M.; Ha, B.-Y.; Liu, A. J. Macromolecules 1999, 32,
3481.
J. Phys. Chem. B, Vol. 104, No. 30, 2000 7081
(22) Kuhn, P. S.; Levin, Y.; Barbosa, M. C. Macromolecules 1998, 31,
8347.
(23) Auer, H.; E.; Alexandrowicz, Z. Biopolymers 1969, 8, 1.
(24) Reddy, M.; Marinsky, J. A. J. Chem. Phys. 1970, 74, 3884.
(25) Takahashi, A.; Kato, N.; Nagasawa, M. J. Chem. Phys. 1970, 74,
944.
(26) Kozak, D.; Kristan, J.; Dolar, D. Z. Phys. Chem. Neue Folge 1971,
76, 85.
(27) Dolar, D. In Polyelectrolytes; Sélegny, E., Mandel, M., Strauss,
U. P., Eds.; Reidel: Dordrecht, 1974; p 97.
(28) Kakehashi, R.; Yamazoe, H.; Maeda, H. Colloid Polym. Sci. 1998,
276, 28.
(29) Oppermann, W.; Wagner, M. Langmuir 1999, 15, 4089.
(30) Cf. the discussion of this point by: Förster, S.; Schmidt, M. AdV.
Polym. Sci. 1995, 120, 53.
(31) Brodowski, G.; Horvath, A.; Ballauff, M.; Rehahn, M. Macromol-
ecules 1996, 29, 6962.
(32) Galda, P., Dissertation, Karlsruhe, 1994.
(33) Guilleaume, B.; Blaul, J.; Wittemann, M.; Rehahn, M.; Ballauff,
M. J. Phys.: Condens. Matter 2000, 12, A245.
(34) Lachenmeyer, K.; Oppermann, W., manuscript in preparation.
(35) Philipopova, O. E.; Rulkens, R.; Kovtunenko, B. I.; Abramchuk,
S. S.; Khokhlov, A. R.; Wegner, G. Macromolecules 1998, 31, 1168.
(36) Le Bret, M.; Zimm, B. H. Biopolymers 1984, 23, 287.
(37) Bieze, T. W. N.; Tromp, R. H.; van der Maarel, J. R. C.; van Strien,
M. H. J. M.; Bellissent-Funel, M. C.; Neilson, G. W.; Leyte, J. C. J. Phys.
Chem. 1994, 98, 4454.
(38) Ha, B.-Y.; Liu, A. J. Phys. ReV. E 1998, 58, 6281.
(39) Dolar, D.; Bester Rogac, M. Acta Chim. SloVak. 1998, 45, 111.
(40) Nagvekar, M.; Tihminlioglu, F.; Danner, R. P. Fluid Phase Equilib.
1998, 145, 15.
(41) Jiang, J.; Liu, H.; Hu, Y. J. Chem. Phys. 1999, 110, 4952.
(42) Lamm, G.; Pack, G. R. J. Phys. Chem. B 1997, 101, 959.