Journal of Colloid and Interface Science 216, 34 40 (1999)
Article ID jcis.1999.6273, available online at http://www.idealibrary.com on
A Study of the Temperature-Dependent Micellization of Pluronic F127
Maria Bohorquez,* Cody Koch,* Troy Trygstad, and Nivedita Pandit ,1
*Department of Chemistry, College of Arts and Sciences, and Department of Pharmaceutical Sciences, College of Pharmacy
and Health Sciences, Drake University, 2507 University Avenue, Des Moines, Iowa 50311
Received November 13, 1998; accepted April 14, 1999
We have examined the temperature-dependent micellization of
the pharmaceutically important PEOPPOPEO copolymer, Plu-
ronic F127, using static light scattering and various aspects of the
pyrene fluorescence spectrum (monomer intensity, excimer forma-
tion and the I 1/I 3 ratio). All techniques gave essentially the same
value for the critical micellization temperatures (cmt) of various
F127 solutions, and our results agreed with those reported in the
literature. Cmt values decrease with increasing F127 concentra-
tion. We observed significant solubilization of pyrene in F127
solutions below the cmt, which was also reflected in the measured
I 1/I 3 ratios. The thermodynamics of the micellization process were
studied and gave different results at low and high F127 concen-
trations. In the low F127 concentration range (up to ;50 mg/mL),
we obtain DH 5 312 kJ mol 21 and DS 5 1.14 kJ mol 21 K 21. Above
50 mg/mL we obtain DH 5 136 kJ mol 21 and a DS 5 0.54 kJ mol 21
K 21. This discontinuity in thermodynamic behavior can be due to
a change in aggregation number with temperature and/or a change
in the micellization process at higher concentrations. 1999
Academic Press
Key Words: Pluronic; poloxamer; triblock copolymer; micelliza-
tion; micelles.
INTRODUCTION
Poloxamers, or Pluronics (BASF), are nonionic, polyoxyeth-
ylenepolyoxypropylenepolyoxyethylene (PEOPPOPEO)
triblock copolymers that have many pharmaceutical applica-
tions. Pluronic F127 (F127), with a nominal molecular weight
of 12,500 and a PEO/PPO ratio of 2:1 by weight, is one of the
most widely used of these copolymers. Aqueous F127 solu-
tions at concentrations of 20% and above show interesting
thermoreversible gelation behavior. This has made F127 at-
tractive in designing thermoreversible gels for many transder-
mal, injectable, and controlled delivery drugs. Since F127
forms micelles and can solubilize hydrophobic compounds,
these gels are attractive for delivering poorly water-soluble
drugs. Thus, an understanding of the micellization and solubi-
lization properties of F127 is very important.
The general micellization behavior of PEOPPO block co-
polymers has been extensively studied, and will not be re-
1
To whom correspondence should be addressed. Fax: (515)-271-1867.
E-mail: nita.pandit@drake.edu.
0021-9797/99 $30.00
Copyright 1999 by Academic Press
All rights of reproduction in any form reserved.
viewed here; the reader is referred to excellent reviews on these
types of block copolymers (13). We focus here on the mi-
cellization of F127, particularly as it relates to pharmaceutical
applications.
In comparison to low-molecular-weight nonionic surfac-
tants, the aggregation behavior of PEOPPOPEO surfactants
like F127 is complex. One key difference that has been con-
sistently reported is that aggregation of Pluronics occurs over
a range of concentrations, rather than at a unique cmc (critical
micelle concentration). As a result, cmc values reported for any
given copolymer can be widely different depending on the
experimental technique used. In several cmc studies, when the
measured property is plotted against copolymer concentration,
two breaks are found, making it difficult to assign a cmc.
These anomalies have been reviewed by Holland et al. (4) and
Alexandridis et al. (5), and are still not completely resolved.
The presence of two or more types of micelles has been
proposed by several workers. Prasad and coworkers (6), study-
ing L62, L64, and F68 by surface tension, proposed that
monomolecular micelles are formed initially, and polymo-
lecular micelles form at higher concentrations. Surface tension
and light scattering studies of P104, P123, and F127 by Wanka
(7) also showed two breaks, ascribed to two critical concen-
trations. A similar explanation was proposed by Turro and
Chung (8) for the aggregation of L-64. Holland et al. (4), using
the fluorescent probe C 12NS and several different poloxamers,
contend that the broad cmc is due to changes in the size, shape,
and polarity of the aggregates over this concentration range,
rather than due to the formation of monomolecular micelles.
However, many of these observations have also attributed to
the inherent polydispersity of Pluronic copolymers (5).
As with all Pluronics, the aggregation of F127 is also
strongly influenced by temperature (2, 4, 6 9). In fact, the
aggregation behavior of Pluronics is most appropriately char-
acterized by a cmc and a cmt (critical micellization tempera-
ture). For example, Rassing and Atwood (6) reported that the
cmc of F127 decreases from 1.75 wt% at 10C to approxi-
mately 0.008 wt% at 30C. Alexandridis et al. (5) used a dye
solubilization method to investigate the cmc of a series of
Pluronics; their results also showed that the cmc of F127
decreases dramatically with temperature.
In view of the importance of F127 in pharmaceutical sys-
34
 TEMPERATURE-DEPENDENT MICELLIZATION OF PLURONIC F127
tems, we were interested in studying the temperature-depen-
dent micellization of F127 further. In particular, we wanted to
study the behavior of a probe molecule in F127 solutions,
because this would mimic a drug molecule in F127 delivery
systems. We were also interested in examining the premicellar
behavior of F127 below the cmt. Wanka et al. (7), using DSC,
surface tension and light scattering, suggested that monomo-
lecular micelles of F127 may exist below a certain critical
temperature, but did not provide conclusive evidence. In any
case, the potential presence of a hydrophobic microenviron-
ment below the cmt is important in the design of pharmaceu-
tical systems because it may provide a suitable region for the
solubilization of nonpolar drugs. We also extended our studies
to higher concentrations of F127 than previously examined,
because it is this higher concentration region that is most often
used in pharmaceutical formulations. It is clear from the pre-
vious discussion that the experimental technique used will
influence the results. We have used static light scattering as a
simple means of detecting the formation of micellar aggre-
gates, and a fluorescent probe to simultaneously study the
polarity of the microenvironment.
The fluorescent probe pyrene has been well-characterized
and has been used to examine the micellization of various other
PEOPPOPEO copolymers (1317). Pyrene is especially The temperature of the sample compartment was controlled
suited for our work because of its well-resolved excitation and
emission spectra, the sensitivity of its emission spectrum to the
polarity of the microenvironment, and its ability to form exci-
mers with a distinct fluorescence.
The emission spectrum of pyrene consists of five primary
bands, normally referred to as I 1 I 5 , from shorter to longer
wavelengths. The ratio of I 1 /I 3 intensities, sometimes called
the Py scale (18), depends strongly on the polarity of the
microenvironment and can be used to provide information
about the micelle interior; the ratio increases with increasing
polarity of the medium. In addition, pyrene can also form
excimers; increasing the concentration of pyrene results in an
increase in excimer formation. The ratio of the fluorescence
intensities of the excimer to monomer (I e/I m) gives information
about the local concentration of pyrene in micelles (13, 19).
Thus, using pyrene as a probe, one can simultaneously study
the polarity of the micelle interior and the distribution of
pyrene in the micelles.
We also concurrently monitored the Rayleigh scattering
intensity as a function of temperature, which gave us an inde-
pendent technique for determining the aggregation behavior of
F127. Alexandridis et al. (17) used a similar approach to study
the micellization of F108 and P104. We did our studies in the
presence and absence of pyrene, to give us an indication of the
extent to which pyrene may perturb the micellization process.
MATERIALS
Pluronic F-127 was purchased from Sigma. Methanol and
polypropylene oxide 3500 (PPO 3500) (Aldrich Chemical
35
Company) were analytical grade. Water was obtained from a
Milli-Q water purification system (Millipore). Pyrene (99%,
Aldrich) was purified by recrystallization from ethanol.
Solution Preparation
Solutions of F127 were made by weighing out the appropri-
ate quantities, adding an appropriate amount of water, and
allowing the solutions to remain in the refrigerator overnight to
ensure complete dissolution. A stock solution of pyrene in
methanol was then added, with its concentration adjusted so
that the final solution contained less than 5% (v/v) methanol.
This level of methanol was found to have no effect on the
spectrum of pyrene in water or in aqueous F127 solutions. All
solutions were stored in the dark in the refrigerator for at least
24 h before fluorescence measurements. This was based on
preliminary results which indicated that it took at least this long
for the system to equilibrate.
Spectroscopy
Fluorescence spectra of pyrene were obtained using a Per-
kin-Elmer LS-50B spectrofluorimeter, at an excitation wave-
length of 336 nm. All spectra were averaged over two scans.
using a refrigerated circulating water bath (Neslab RTE 100)
and the actual temperature of the sample in the cuvet was
measured using a Fisher Scientific traceable digital thermom-
eter. Samples were preequilibrated at the experimental temper-
ature and then placed in the sample compartment. For fixed
temperature studies, the temperature was maintained constant.
For experiments where the temperature was varied, the water
bath was programmed to increase temperature at a rate of
approximately 11.5C/min. The fluorimeter was run in a time
drive mode, and the intensities of the Rayleigh (336 nm),
monomer (374 and 385 nm), and excimer (460 nm) bands were
measured as a function of time. The temperature of the sample
solution in the cuvet was also measured periodically during this
process. Thus, fluorescence intensities and sample temperature
could be measured simultaneously as a function of time while
temperature increased. For a few samples, the direction of the
temperature change was reversed, and the experiment carried
out while the solution cooled over time. The results were the
same as when the sample was heated, showing that there was
no hysteresis in the measurements and that equilibrium was
established in our systems as temperature was changed.
RESULTS
Determination of cmt Using Static Light Scattering
We examined the static scattering of various F127 solutions
by monitoring the Rayleigh peak as a function of temperature.
For dilute solutions, the light scattering intensity should be
indicative of the weight average aggregation number of the
36 BOHORQUEZ ET AL.

FIG. 1. Light scattering intensity as a function of temperature for typical FIG. 2. The steady state emission spectra (l exc 5 336 nm) of 1.07 3 10 24
F127 solutions. The cmt is determined from the intersection of the two fitted M pyrene in solutions containing various concentrations of F127 at 24C.
straight lines.

diverted to excimer formation, the intensities of the monomer

micelles. Figure 1 shows the light scattering intensity as a
function of temperature for solutions of varying F127 concen-
tration. It is apparent that there is a distinct temperature at
which scattering intensity increases dramatically, reflecting the
formation of micelles. The temperature at which this break in
the curve occurs can therefore be designated as the cmt.
Since we intended to use pyrene as a probe in later experi-
ments, we examined the scattering profiles in both the presence
and the absence of pyrene and found no significant difference
in the results. This may indicate that pyrene at these concen-
trations does not perturb the micellization process significantly
or that the technique cannot detect the changes that may be
occurring in the presence of pyrene.
bands decrease, while the intensity of the excimer band in-
creases. This decrease in monomer intensities with Pluronic
concentration is similar to that reported by Kabanov (15) for
P85-pyrene systems.
Figure 3 is a plot of the I 1 /I 3 and I e/I 3 ratios, obtained from
Fig. 2, as a function of F127 concentration at 24C. The I e/I 3
decreases with F127 concentration because, as more micelles
are formed, the effective concentration of pyrene in each
micelle is reduced. The I 1 /I 3 ratio at 25C is essentially inde-
pendent of F127 concentration, indicating that the interiors of
the micelles formed in all these solutions have essentially the
same micropolarity at 25C.

Pyrene Emission Spectra in F127 Solutions

The steady state emission spectra (l exc 5 336 nm) of
1.067 3 10 24 M pyrene in solutions containing various con-
centrations of F127 at 24C are shown in Fig. 2. The 350- to
420-nm region of these spectra corresponds to the pyrene
monomer, and the vibrational fine structure represents the local
polarity experienced by pyrene. The broad structureless band
with a maximum at 460 nm represents excimer fluorescence.
Excimer formation is sensitive to pyrene concentration because
it involves an interaction between two pyrene species. A spec-
trum in the absence of F127 is not included in Fig. 1 because
of the extremely limited solubility of pyrene (;10 27 M) in
water in the absence of F127; excimer formation is not seen at
such low concentrations. The F127 solutions depicted in Fig. 2
have cmt values below 24C, as shown by our scattering
results, and thus micelles are expected to be present. These
micelles provide a hydrophobic environment into which the
pyrene partitions, and the local micellar pyrene concentration FIG. 3. Plot of the I 1 /I 3 and I e/I 3 ratios as a function of F127 concentra-
is high enough to form excimers. As pyrene molecules are tion at 24C.
 TEMPERATURE-DEPENDENT MICELLIZATION OF PLURONIC F127
FIG. 4. I 1 /I 3 ratio of 2 3 10 25 M pyrene in water, PPO 3500, and 20
mg/mL F127, as a function of temperature.
Determination of cmt Using the I 1/I 3 Ratio
We now report the results of studies where pyrene fluores-
cence was examined as a function of temperature. By exam-
ining the pyrene monomer and excimer intensities simulta-
neously with temperature, we can obtain information about the
polarity of the environment around pyrene and the local con-
centration of pyrene in the micelles.
Let us first consider the pyrene monomer spectrum. The
I 1 /I 3 ratio of pyrene as a function of temperature can be used
to directly determine the cmt of F127 at different concentra-
tions. We carried out these experiments at several F127 con-
centrations between 10 and 100 mg/mL. Figure 4 shows the
I 1 /I 3 ratio of 2 3 10 25 M pyrene as a function of temperature
for 20 mg/mL F127 solutions. For comparison, we also show
the ratio in water and in PPO 3500 as solvents is also shown.
The change of I 1 /I 3 in water and PPO is similar to that seen in
other similar homogeneous solvents (17). PPO 3500 was se-
lected because its molecular weight is similar to that of the
PPO segment in F127.
For F127 solutions at low temperatures, where no micelles
are present, I 1 /I 3 reflects the predominantly aqueous microen-
vironment around the pyrene, and I 1 /I 3 is high. It is interesting
to note that the solubility of pyrene in F127 solutions is
significantly higher than that in water, even in the absence of
micelles. This allowed us to carry out experiments with ;2 3
10 25 M pyrene over the entire temperature range. In addition,
the I 1 /I 3 ratio in F127 solutions below the cmt is lower than
that in water. Both these observations indicate that the micro-
environment around pyrene is less polar than pure water, even
below the cmt. Our results also show that the initial I 1 /I 3 ratio
decreases with increasing F127 concentration, due to a pro-
gressively less polar microenvironment.
As temperature increases, I 1 /I 3 begins to decrease sharply,
indicating that the microenvironment around pyrene is becom-
37
ing even more nonpolar. The sigmoidal graph then essentially
levels off. This final ratio is consistent with a medium polarity,
approaching but not reaching that of PPO 3500, indicating that
the micelle interior is more polar than PPO 3500.
On comparison of these results with the light scattering data
in Fig. 1, we find that the break in Fig. 1 coincides with the
inflection point of Fig. 4, rather than with either the first or
second break in the I 1 /I 3 curve. This means that the local
polarity around the pyrene begins to decrease significantly
before micelles are observed. Alexandridis et al. (17) con-
ducted similar investigations with P104 and F108, and also
found that the cmt occurs at the inflection point of the transition
region, because this temperature agreed with the results ob-
tained from their dye solubilization experiments. The first
break in Fig. 4 may be due to the potential polydispersity of the
F127 sample. The presence of few particularly hydrophobic
polymer molecules may provide a microenvironment that is at
least partially sensed by pyrene. On the other hand, this initial
break occurs due to dehydration of the PPO segments, provid-
ing an increasingly nonpolar environment for pyrene and re-
sulting in a lower I 1 /I 3 ratio. In fact, the presence of a hydro-
phobic probe molecule may even initiate this reorganization.
Our results cannot distinguish between these possibilities. Nev-
ertheless, our results show that a hydrophobic molecule, such
as a drug, may be substantially solubilized in F127 solutions
below the cmt.
As temperature is further increased, the PPO segments con-
tinue to dehydrate, causing a progressive decrease in the po-
larity around pyrene. Eventually, the dehydration is sufficient
to form micelles at the inflection point in the curve, which
represents the cmt. The further decrease in I 1 /I 3 can be attrib-
uted to the continued expulsion of water from the micelle
interior, making it more nonpolar. The final I 1 /I 3 ratio does not
reach that of pure PPO 3500, indicating that some water may
still be present in the micelle.
The final or limiting I 1 /I 3 ratio was also found to decrease as
F127 concentration increases. Since this ratio is a measure of
the polarity of the micelle interior, it appears that, at higher
F127 concentrations, the micelle interior is more nonpolar. It is
interesting that this happens in spite of the cmt being lower at
higher F127 concentrations, since the PPO segments would be
expected to be more hydrated at lower temperatures.
Determination of cmt Using the I e /I 3 Ratio
Let us now consider the I e/I 3 ratio and its dependence on
temperature. Figure 5 shows I e/I 3 as a function of temperature
for the same selected systems shown in Fig. 6; 2 3 10 25 M
pyrene in 10 and 100 mg/mL F127 solutions. Similar profiles
have been reported for the micellization of another Pluronic
copolymer (13). At low temperatures, when micelles are not
present, there is essentially no excimer formation because
pyrene is homogeneously distributed in the solution and the
concentration is not high enough for excimer formation. As
38 BOHORQUEZ ET AL.

TABLE 1
Cmt (C) Values for the Micellization of F127
Obtained by Various Approaches

F127 Light I 1 /I 3 I e/I 3 I3

(mg/mL) scattering inflection pt. maximum break

5 25.7 26.0 25.9

10 24.2 24.8 24.1
20 23.7 23.1 23.3 22.5
40 21.9 21.1 20.7 20.5
60 20.5 20.0 20.1 19.9
80 18.4 18.9 18.7
100 17.8 17.5 17.1 17.0

Determination of cmt Using I 3 Intensities

FIG. 5. I e/I 3 ratios of 2 3 10 25 M pyrene as a function of temperature in
10 and 100 mg/mL F127 solutions.
temperature is increased, the I e/I 3 ratio gradually increases,
presumably due to an increase in the effective concentration
of pyrene in localized areas. The I e/I 3 ratio peaks at a certain
temperature indicating that the effective concentration
pyrene is the largest, and maximum excimer formation is seen.
As temperature is increased further, excimer formation de-
creases, indicating that pyrene molecules are once again dis-
tributed in a large effective volume of medium.
This behavior is also suggests some localization of pyrene
below the cmt to permit excimer formation. When a few
micelles are first formed, we see maximum excimer formation,
followed by a decrease in I e/I 3 as the number of micelles
increases. The temperature at which the maximum in I e/I 3
occurs corresponds to the inflection point in the I 1 /I 3 curve
(Fig. 4), which lends support to this argument.
The examination of the fluorescence intensities of the mono-
mer peaks as a function of temperature is also interesting,
although more complex to interpret. This is because intensity
depends not only on pyrene concentration, but on the polarity
and viscosity of the pyrene microenvironment. Nevertheless,
we can use the variation of monomer and excimer intensity
with temperature to determine the cmt of F127 solutions.
Figure 6 shows a typical plot of I 3 and I e as a function of
temperature, in this case for 2 3 10 25 M pyrene in 20 mg/mL
F127.
At low temperature, pyrene is in an aqueous environment
and shows a low monomer intensity and no excimer. As
temperature is increased, we observe a gradual increase in
monomer and excimer intensities, indicating that pyrene is
experiencing an increasingly nonpolar microenvironment, and
is becoming somewhat localized. When micelles form at the
cmt, excimer intensity shows a maximum, and the monomer
intensity shows a sharp increase, reflecting the higher quantum
yield of pyrene in the micelle interior. The continued increase
in I 3 reflects the progressive dehydration of the micelle inte-
rior, and the formation of more micelles. I e decreases as
expected over this range because of dilution of pyrene in the
micelles. When the structure of the micelle stabilizes, I 3 de-
creases with temperature as expected in a homogeneous sol-
vent.
Table 1 lists a comparison of cmt values obtained from all of
the approaches we have described, and Fig. 7 shows these
results graphically.

Thermodynamic Analysis

The standard free energy for micellization (DG) for non-

ionic surfactants is usually given by the expression

DG 5 RT ln~X cmc!, [1]

FIG. 6. I 3 and I e intensities as a function of temperature for 2 3 10 25 M
pyrene in 20 mg/mL F127. where R is the universal gas constant, T cmt is the cmt, and X cmc
 TEMPERATURE-DEPENDENT MICELLIZATION OF PLURONIC F127 39

Pluronics, also found that F68, F88, and F108 showed such a
discontinuity, all at concentrations above about 5% (w/v), or 50
mg/mL, as in our case. This was explained as a breakdown of
the assumptions inherent in the thermodynamic analysis at
higher concentrations of these copolymers. At these concen-
trations, entanglement of the hydrated PEO chains begins to
occur for these hydrophilic, higher molecular weight polymers,
thus perhaps altering the micellization process. Since F127 is
also a high-molecular-weight, hydrophilic Pluronic, and is
known to form rigid gels at concentrations of 200 mg/mL, such
entanglements may well occur at concentrations in the 50 100
mg/mL range and contribute to the discontinuity in Fig. 8.

CONCLUSIONS

We have conducted a detailed examination of the tempera-

FIG. 7. Values of the cmt as a function of F127 concentration, as deter- ture-dependent micellization behavior of Pluronic F127, a
mined by various approaches. pharmaceutically important surfactant and polymer. We have
shown that pyrene fluorescence can be used to measure the cmt
of F127 by a variety of approaches. Our results show that
is the corresponding cmc in mole fraction units. This equation hydrophobic molecules may be substantially solubilized in
can be rearranged to give F127 solutions prior to micelle formation, which is relevant for
the solubilization of hydrophobic drugs. For pyrene, this sol-
1/T 5 ~R/DH!ln X cmc 1 DS/DH. [2] ubilization was observed at approximately 12C below the
cmt. Although this temperature difference appears small, it
Such an analysis has been used to obtain thermodynamic indicates that changes in body temperature (which are usually
constants for the micellization of Pluronics (5). Figure 8 shows of the order of 15F) may have an effect on the behavior of
ln X cmc versus 1/T plots for the micellization of F127, using all F127 systems. We have also shown that the thermodynamics of
our results. It is apparent that the data do not fall on one the micellization process may change at higher F127 concen-
straight line; low and high concentration ranges of F127 appear trations, due to either changes in aggregation number and/or
to show different thermodynamic behavior. This has been progressive entanglements between PEO chains. Further work
observed for a few other Pluronic copolymers (5). In the low will examine the solubilization of other hydrophobic molecules
F127 concentration range (up to about 4 mM or 50 mg/mL), below the cmt, the thermodynamics at even higher concentra-
the data appear linear, and we obtain DH 5 312 kJ mol 21 from tions of F127 where gel formation occurs, and changes in
the slope and a DS 5 1.14 kJ mol 21 K 21 from the intercept. In aggregation number with concentration and temperature.
comparison, Alexandridis et al. (5) reported values of DH 5
253 kJ mol 21 and DS 5 0.944 kJ mol 21 K 21, for the concen-
tration range between 0.02 mM (0.25 mg/mL) and 3.97 mM
(49.6 mg/mL). Our studies give different values above 50
mg/mL; DH 5 136 kJ mol 21 and DS 5 0.54 kJ mol 21 K 21 for
the concentration range between 50 and 100 mg/mL.
One of the assumptions in using Eqs. [1] and [2] is that the
aggregation number remains constant over the temperature and
concentration ranges studied. It is generally accepted (10, 20)
that the aggregation number of Pluronic micelles does not
change with concentration, but increases with temperature. The
strong variability in the aggregation numbers reported, how-
ever, makes it difficult to use these values to interpret our
results. The cmt values of our solutions changed by about 9C
over the concentration range of 5100 mg/mL, and the change
in the aggregation number over this range is probably small but
significant. This could be at least partially responsible for the
discontinuity in our plot. Alexandridis et al. (5), in doing a
similar analysis on the micellization themodynamics of several FIG. 8. Thermodynamic plot for the micellization of F127.
40 BOHORQUEZ ET AL.

REFERENCES 10. Linse, P., and Malmsten, M., Macromolecules 25, 5434 (1992).
11. Malmsten, M., and Lindman, B., Macromolecules 25, 5440 (1992).
1. Nace, V. M. (Ed.) Non-Ionic Surfactants: Polyoxyalkylene Block Co- 12. Linse, P., Macromolecules 26, 4437 (1993).
polymers, Surfactant Science Series, Vol. 60. Dekker, New York, 1996. 13. Turro, N., and Kuo, P., Langmuir 2, 438 (1986).
2. Chu, B., and Zhou, Z., Surf. Sci. Ser. 60, 67 (1996). 14. Almgren, M., Alsins, J., and Bahadur, P., Langmuir 7, 446 (1991).
3. Alexandridis, P., and Lindman, B. (Ed.), Amphiphilic Block Copolymers: 15. Kabanov, A., Nazarova, I., Astafieva, I., Batrakova, E., Alakhov, V.,
Self Assembly and Applications. Elsevier Science, Amsterdam, 1997. Yaroslavov, A., and Kabanov, V., Macromolecules 28, 2303 (1995).
4. Holland, R., Parker, E., Guiney, K., and Zeld, F., J. Phys. Chem. 99, 11981 (1995). 16. Nivaggioli, T., Alexandridis, P., Hatton, T., Yekta, A., and Winnik, M.,
5. Alexandridis, P., Holzwarth, J., and Hatton, T., Macromolecules 27, 2414 Langmuir 11, 730 (1995).
(1994). 17. Alexandridis, P., Nivaggioli, T., and Hatton, T., Langmuir 11, 1468
6. Prasad, K., Luong, T., Florence, A., Paris, J., Vaution, C., Seiller, M., and (1995).
Puisieux, F., J. Colloid Interface Sci. 69, 225 (1979). 18. Dong, D., and Winnik, M., Can. J. Chem. 62, 2560 (1984).
7. Wanka, G., Hoffmann, H., and Ulbricht, W., Macromolecules 27, 4145 (1994). 19. Nivaggioli, T., Tsao, B., Alexandridis, P., and Hatton, T., Langmuir 11,
8. Turro, N., and Chung, C., Macromolecules 17, 2123 (1984). 119 (1995).
9. Rassing, J., McKenna, W., Bandopadhyay, S., and Eyring, E., J. Mol. Liq. 20. Wanka, G., Hoffmann, H., and Ulbricht, W., Colloid Polym. Sci. 268, 101
27, 165 (1984). (1990).