Article

pubs.acs.org/Macromolecules

Collapse-to-Swelling Transitions in pH- and Thermoresponsive

Microgels in Aqueous Dispersions: The Thermodynamic Theory
Alexey A. Polotsky,† Felix A. Plamper,‡ and Oleg V. Borisov†,§,⊥,*
†
Institute of Macromolecular Compounds of the Russian Academy of Sciences, 31 Bolshoy pr., 199004 St.-Petersburg, Russia
‡
Physikalische Chemie II, RWTH Aachen University, 52056 Aachen, Germany
§
St.Petersburg National Research University of Information Technologies, Mechanics and Optics, 197101, Kronverkskiy pr., 49,
St.Petersburg, Russia
⊥
Institut des Sciences Analytiques et de Physico-Chimie pour l’Environnement et les Matériaux, UMR 5254 CNRS/UPPA, Pau,
France

ABSTRACT: We present a theory of a conformational

collapse-to-swelling transition that occurs in aqueous dis-
persions of multiresponsive (pH- and thermoresponsive)
microgels upon variation of ionic strength, temperature, or
pH. Our theory is based on osmotic balance arguments and
explicitly accounts for ionization equilibrium inside microgel
partices. The theory predicts complex patterns in the
dependence of the microgel particle dimensions on the control parameters: An increase in temperature leads to worsening of
the solvent quality for the gel forming LCST-polymers and to concomitant decrease in the dimensions of the gel particles. This
collapse of the gel particles provoked by an increase in temperature occurs either smoothly (at high or low ionic strength), or
may exhibit a jump-wise character at intermediate ionic strength. The theory further predicts that the degree of swelling of
microgel particles varies nonmonotonously and exhibits a maximum as a function of salt concentration at a pH close to the pK.
This nonmonotonous variation of the particle dimensions occurs continuously at temperatures below or slightly above LCST
(good or marginal poor solvent strength conditions, respectively), whereas at higher temperatures the jump-wise swelling of the
gel particles is followed by either continuous or jump-wise collapse induced by progressive increase in the salt concentration. A
decrease/increase in pH leads to deswelling of the weak polyacid/polybase gel particles, which occurs smoothly at temperatures
below LCST, but may exhibit a discontinuity above LCST. These theoretical predictions can be used for design of smart stimuli-
responsive microgels.

I. INTRODUCTION circumstances are known where the macroscopic size of gels is

The ability of ionic polymers (polyelectrolytes) to change their
conformations under the action of external triggers, such as
ionic strength and pH, is exploited in many applications ranging
from oil recovery and paper-making to nanotechnology and
nanomedicine. A remarkable progress in understanding the
properties of linear1,2 and branched3 polyelectrolytes has been
achieved in the past few years.
There are important distinctions in properties of strong
(quenched) and weak (annealing) polyelectrolytes. In a strong
polyelectrolyte the fraction α of charged monomer units is fixed
chemically and does not depend on the environmental
conditions. In a weak polyelectrolyte the fraction α of charged
monomer units coincides with the degree of ionization and is
governed by the local pH which may noticeably differ from the
pH of the buffer.4 The latter is especially true for branched
polyelectrolytes3 and ionic gels.
Hereby, polyelectrolyte gels can be regarded as a special class
of branched ionic polymers. Because of osmotic pressure of the
confined counterions, they exhibit often tremendous swelling in
solvents of high dielectric constant like water, while still having
a defined macroscopic shape. The swelling is especially
pronounced when it comes to highly charged gels. Generally,
detrimental. E.g., the characteristic switching time is propor-
tional to the surface of the gel.5 Therefore, gels in the
nanometer to micrometer scale can provide beneficial switching
kinetics and rapid uptake/release of guest molecules. These gels
are termed as microgels6−8 and will be regarded within this
investigation.
In presence of additional attractive (solvophobic) inter-
actions, discontinuous volume transitions in the ionic hydrogels
can appear. This means that large effects in the swelling can be
observed when only small changes in the solvent strength are
applied.9−11 The ion pair formation in less polar medium may
provide additional driving force for the discontinuous gel
collapse.12−15
These examples indicate that polyelectrolytes and the gels
thereof are interesting species. A subtle balance between
attracting and repellant interactions appears to offer this rich
behavior. Therefore, the use of weak polyelectrolytes with
Received: July 4, 2013
Revised: September 18, 2013
Published: October 24, 2013

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Macromolecules
tunable charge and hydrophilicity might envision further
stimuli-responsiveness for future applications.
There are literature reports on the stimuli-responsive
behavior of the microgels formed by poly(acrylic acid) (PAA)
or different kinds of copolymers including monomer units of
acrylic acid.16,17 The swelling behavior of these weak
polyelectrolyte microgel particles can be efficiently controlled
by pH: a decrease in pH causes a decrease in the degree of
ionization of the microgel particles, drop in the intragel osmotic
pressure of the counterions and concomitant collapse of the
microgel.
In contrast to pure PAA, poly(N,N-dimethylaminoethyl
methacrylate) (PDMAEMA) and especially copolymers of N-
isopropylacrylamide (NIPAM) and its derivatives exhibit
additional thermosensitive features.18−21 That is, the polymer
is soluble in water under ambient conditions but the solubility
decreases upon an increase in temperature. Hence, aqueous
solutions of such polymers exhibit lower critical solution
temperature (LCST): Below the LCST the polymer is soluble
at any concentration, while above LCST macroscopic phase
separation into dilute and concentrated phases (precipitate)
may occur.22 Regarding microgels, collapse of the microgel
particles dispersed in aqueous media occurs upon an increase in
temperature above LCST which can be termed in this case as
volume phase transition temparature (VPTT).6 Remarkably,
the microgel dispersions may exhibit colloidal stability even at
temperature above VPTT.
We have already revealed23,24 an interplay between
protonation and thermoresponsive behavior in case of linear
and branched PDMAEMA. Dependent on the pH, PDMAEMA
turns water-insoluble upon heating. Furthermore, microgels of
PDMAEMA show an excellent pH-responsiveness. Charged
thermosensitive microgels of PDMAEMA have been pre-
pared.25,26 Otherwise, cationic or anionic monomers can be
copolymerized with monomers (like NIPAM) yielding
thermosensitive polymers.18,19,27 For both weak and strong
polyelectrolytes, the swelling of the gel particles can be
manipulated by changing the strength of electrostatic
interactions by, e.g., addition of salt ions.28 For weak
polyelectrolytes pH can be considered as additional control
parameter since its variation enables a tuning of the charge of
the gel particles. In addition, issues of colloidal stability of the
microgel dispersion might arise.29
Concluding, the combination of pH and thermosensitive
properties of, e.g., PDMAEMA makes the stimuli-responsive
behavior of the microgel more sophisticated, especially when it
comes to the salt dependence. Indeed, such complex patterns as
re-entrant swelling-to-collapse transitions provoked by increas-
ing salt concentration were predicted theoretically30,31 and
observed experimentally32−34 for pH-sensitive polyelectrolyte
brushes and for star-branched polyelectrolytes.35,36 The non-
monotonous salt dependence of the degree of swelling of pH-
sensitive branched polyions (or polyelectrolyte brushes) was
explained by dual effect of added salt on the differential
intramolecular osmotic pressure: the initial increase in salt
concentration provokes an increase in the osmotic pressure due
increasing ionization of the monomer units, whereas further
increase in salt concentration leads to a leveling off of the
concentrations of small ions inside the star (or in the brush)
and in the solution and to a concomitant decrease in the
differential osmotic pressure. More recent studies based on
more advanced theoretical approaches37,38 have enabled a
detailed analysis on the internal structural rearrangements
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occurring in pH-sensitive polyelectrolyte brushes upon
variation of salt concentration. Furthermore, combined effects
of added salt and tunable hydrophobicity of the monomer units
on conformations of pH-sensitive star-branched polyelectro-
lytes were recently investigated.39,40 It was demonstrated, that
salt-induced re-entrant swelling-to-collapse intramolecular
conformational transitions in star-branched hydrophobic
polyions occur continuously either at high or at low ionic
strength but may exhibit features of a first-order phase
transition (i.e., intramolecular microphase separation) at
intermediate salt concentration.
The aim of the present paper is to investigate volume
transitions occurring in dilute aqueous dispersions of multi-
responsive (pH- and thermoresponsive) microgel particles
upon variation of external parameters, such as temperature,
ionic strength and pH. The latter two affect the strength of
Coulomb interactions between charged monomer units,
whereas temperature controls the strength of short-range
excluded volume interactions (solubility of the polymer in the
absence of charges). In addition, hydrostatic pressure might be
considered as additional parameter, which affects the strength
of excluded volume interactions and thus solubility of the
monomer units of the microgel in water.41−43 As we
demonstrate below, a competition of short-range attractive
and long-range repulsive interactions with ionization equili-
brium inside the gel leads to complex patterns in the
dependence of the microgel particles dimensions on these
three control parameters even in the absence of any polymer-
or ion-specific interactions in the system. Hence, our
conclusions are relevant for a wide class of thermosensitive
weak polyelectrolyte microgels, and enables one to rationalize
stimuli-responsive behavior of e.g. microgels of PNIPAM with
pH-sensitive ionic comonomers or PDMAEMA in aqueous
dispersions.
II. MODEL AND FREE ENERGY
Our approach is based on the analysis of the Gibbs free energy
of a swollen microgel particle (calculated per subchain) which
can be presented in a mean-field approximation as
F = Fconf + Fex . vol + Fion (1)
The first term in eq 1 accounts for conformational free energy
of a stretched subchain comprising N monomer units and
extended up to the size R
3R2
Fconf /kBT =
2Nb2 (2)
where kB is the Boltzmann constant and T is the temperature.
Here we assume that subchains are extended with respect to
ideal (Gaussian) dimensions, exhibit Gaussian elasticity and are
intrinsically flexible, that is, the statistical segment length is on
the order of the monomer unit length b. The condition of the
subchain extension, R ≥ bN1/2, may be violated in the microgel
particles collapsed in poor solvent. The corresponding
correction term which accounts for conformational entropy
losses in contracted subchains could be introduced following
the lines of ref 44. This correction, however, is negligible
compared to other contributions to the free energy in the
collapsed state and does not qualitatively affect the results of
our analysis.
The subchain dimension R is related to the polymer volume
fraction c in the microgel as
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Macromolecules
qNb3 QNb3
c= = length lB = e2/ϵkBT (here ε is the dielectric constant of the
2R3 V (3)
where q is the number of subchains emanating from a junction
point, Q is the number of subchains and V is the volume of the
microgel particle.
The free energy of nonelectrostatic (excluded volume)
interactions can be presented in the virial approximation as
Fex . vol /kBT = N (vc + wc 2) (4)
where v and w are the second and the third virial coefficients,
respectively. The second virial coefficient (the excluded volume
parameter) v can be tuned by variation in the temperature. For
most of the water-soluble polymers (including PNIPAM and
PDMAEMA), v is a decreasing function of the temperature:
vT≤LCST ≥ 0 and vT≥LCST ≤ 0 correspond to good and poor
solvent conditions, respectively, whereas vT=LCST = 0 corre-
sponds to the Θ-point. In the vicinity of LCST the second virial
coefficient is expected to vary approximately linearly as a
function of temperature, v ∼ (LCST − T). An increase in
pressure at constant temperature is known to improve solubility
of polymer in water,41 that is, v should be an increasing function
of pressure. On the contrary, the third virial coefficient is
virtually independent of temperature, w = const. It is known,
that solubility of nonionic polymers, like e.g. PNIPAM in water
is affected by salt concentration,45 that is, the second virial
coefficient v may exhibit a dependence on the ionic strength. In
our analysis we, however, disregard this dependence because of
the primary effect of salt concentration on the strength of ionic
interactions acting between charged monomer units of a pH-
sensitive microgel. We also disregard possible dependence of v
on the pH of the solution, which may take place in the case of,
e.g., hydrogen bond formation between nonionized monomer
units.
The ionic contribution to the free energy is specified in the
framework of the local electroneutrality approximation, i.e., by
assuming that the charge density of ionized monomer units
inside the gel is locally compensated by excess density of
mobile counterions. With the account of equilibrium exchange
of mobile ions between microgel volume and the surrounding
solution (where concentrations of all mobile ion species are
assumed to be fixed), the ionic contribution to the Gibbs free
energy is specified as3
⎧ ⎡ ⎤⎫
⎪ ⎛ αc ⎞ 2 ⎪
Fion(c)/kBT = N ⎨ln(1 − α) − ⎢ 1 + ⎜ ⎟ − 1⎥⎥⎬
cs ⎢
⎪ c
⎣ ⎝ cs ⎠ ⎦⎪
⎩ ⎭
(5)
where cs is the overall concentration (volume fraction) of
monovalent ion species (including H+ and OH− ions and added
monovalent salt) in the solution.
The local electroneutrality approximation is justified for
dilute dispersions of ionic microgels with or without added
electrolyte provided that the size of the gel particles is
sufficiently large to ensure that the major fraction of mobile
counterions is retained by the Coulomb attraction inside the
microgel particles. The solution of the corresponding Poisson−
Boltzmann equation for a branched polyion (e.g., a microgel
particle) placed into an electroneutral Wigner−Seitz cell46,47
proves, that with the accuracy of logarithmic factors, the
elecrtroneutrality condition is fulfilled if the bare charge of the
microgel particle, αNQ, (measured in elementary charges e) is
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larger than its characteristic size V1/3 reduced by the Bjerrum
medium). Since for the microgel particle V scales proportion-
ally to Q and the dimensions of a subchain in the low salt limit
can be estimated as ∼ α1/2Nb, the microgel particles comprising
Q ≫ (α−1/2b/lB)3/2 subchains can be considered as almost
electroneutral. Hence, the local electroneutrality condition
applies with a good accuracy to sufficiently large microgel
particles, with the typical particle size on the order of 100 nm
or larger. It is essential, however, that volume fraction occupied
by the gel particles in the solution is sufficiently small to ensure
quasi-constant values of chemical potentials of all mobile ion
species.
The degree of ionization α of subchains in the microgel
depends on the local pH inside the gel, which in turn depends
on the pH in the buffer and on the excess local electrostatic
potential in the gel. By combining the mass action law with the
local electroneutrality condition the degree of ionization α of
the gel can be expressed as3
⎛ αc ⎞ 2
α 1 − αb αc
= 1+⎜ ⎟ −
1 − α αb ⎝ cs ⎠ cs (6)
The degree of ionization αb of the respective nonpolymeric
ionizable groups in bulk solution is related to pH of the buffer
solution as
αb = (1 + 10±(pH − pK ))−1 (7)
where pK = −log K, and K is the ionization constant of a single
ionizable group and signs “+” and “−” refer to cationic and
anionic microgels, respectively.
It is convenient to characterize the extent of swelling of the
microgel particles by the dimensionless parameter
R ⎛ c ⎞1/3
= ⎜ θ ⎟ ≡ β1/3
Rθ ⎝c⎠
where
R θ = N1/2bw1/8q1/4 2−1/8
and
(q/2)1/4
cθ =
N1/2(2w)3/8
are respectively the subchain dimensions and the volume
fraction of polymer in the microgel at the Θ-temperature (i.e.,
at v = 0) in the absence of ionic interactions. Assuming that in a
dry state the volume fraction of polymer in the microgel equals
unity, we can express the degree of swelling as R/Rdry = β1/3·
N1/6(2w)1/8(q/2)−1/12.
Below we characterize the temperature-controlled solvent
strength using the dimensionless parameter τ/cθ, where τ = −v/
2w. An increase in temperature leads to a decrease in v and to
an increase in τ. Under poor solvent conditions, v ≤ 0, τ
coincides with the volume fraction of polymer in the precipitate
(or in a large polymer globule48).
The average number N of monomer units in a subchain is
inversely proportional to the degree of cross-linking and can be
considered as a variable architectural parameter of the gel. An
increase in N is manifested in a decrease in cθ. Below we shall
analyze how the pH-/thermo-responsive properties of the
microgels depend on the degree of cross-linking.
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Figure 1. Dependences of the reduced size of the microgel particle R/Rθ (a) and degree of ionization α (b) on reduced temperature τ/cθ for N = 20,
q = 4, αb = 0.6 and different salt concentrations.

The equilibrium degree of swelling of the microgel particle contraction of the gel occurs continuously upon a decrease in
with respect to the Θ-dimensions, R/Rθ  β1/3 obeys the the solvent strength. For weak (pH-sensitive) polyelectrolyte
following equation, which results from minimization of the gels, the degree of ionization of the subchains depends on the
Gibbs free energy determined by eqs 1, 4, 5 and 6: polymer concentration inside the gel and on the ionic strength
⎡ ⎤ in the surrounding solution, eq 6. Therefore, the temperature-
8/3 τ cs 3⎢ ⎛ αc θ ⎞ 2 ⎥ induced collapse transition in such microgels acquires novel
β + β− β 1+⎜ ⎟ − 1⎥ = 1
cθ 2wcθ3 ⎢⎣ ⎝ csβ ⎠ ⎦
features.
(8) Figure 1a illustrates how the character of the temperature-
induced collapse transition changes upon variations in salt
where the degree of ionization α is given by
concentration cs. The microgel gets contracted continuously as
⎛ αc ⎞ 2 a function of decreasing solvent strength (increasing temper-
α 1 − αb αc
= 1 + ⎜ θ⎟ − θ ature) at low or high salt concentrations, but exhibits a jump-
1 − α αb ⎝ csβ ⎠ csβ (9) wise collapse below the Θ-point (above LCST) in the
intermediate range of salt concentrations. This discontinuity
The free energy of the microgel (per subchain) can be is also reflected in the temperature dependences of the degree
expressed as of ionization, presented in Figure 1b. At any salt concentration
F cs an increase in temperature (in τ) leads to compactization of
2wcθ 2NkBT the microgel particles and thus provokes a concomitant
decrease in degree of ionization α. Indeed, α is a monotonously
⎡ ⎤
5 2/3 1 cs ⎢ ⎛ αc θ ⎞ 2 ⎥
decreasing function of polymer concentration, eq 6, since
= β − − β 1 + ⎜ ⎟ − 1 repulsive electrostatic interactions of charged monomer units
2 2β 2 wcθ 3 ⎢⎣ ⎝ csβ ⎠ ⎥
⎦ hinder ionization. Therefore, the degree of ionization in the
(10)
collapsed state is much smaller than that in the swollen state.
In the first order transition point the polymer density and the In Figure 2 the critical value of the bulk degree of ionization,
ionization degree in the coexisting collapsed and swollen states αb,crit(cs), is presented as a function of salt concentration. At
(denoted as state 1 and state 2) are determined from the each given salt concentration cs the temperature-induced
condition contraction of the microgel particles occurs continuously, if
F(β1 , α1) = F(β2 , α2) (11) the bulk degree of ionization αb ≤ αb,crit(cs). On the contrary, at

solved together with eqs 8, 9. The critical line in (αb, cs) plane
separating the ranges of continuous and discontinuous
temperature induced collapse transitions is obtained from the
condition
dτ(β)/dβ = d2τ(β)/dβ 2 = 0 (12)

III. RESULTS
A. Temperature-Induced Swelling-to-Collapse Tran-
sition. An increase in temperature leads to a decrease in
solubility (enhancing hydrophobicity) of polymer chains
forming the microgel and, as a result, to deswelling of the gel
particles. This deswelling is, however, opposed by excess
osmotic pressure of the mobile ions inside the gel. For a
microgel with permanent charges (strong polyelectrolytes) in
salt-free solution the competition of increasingly strong short- Figure 2. Critical value of the bulk degree of ionization αb,crit vs salt
range monomer−monomer attractions with the osmotic concentration calculated for different values of N, as indicated in the
pressure of confined counterions results in a jump-wise collapse Figure. At αb ≥ αb,crit the temperature-induced collapse of the microgel
transition, whereas at sufficiently high ionic strength the occurs as a jump-wise first order phase transition.

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Macromolecules
Figure 3. Dependences of reduced size of the microgel particle R/Rθ (a) and degree of ionization α (b) on reduced salt concentration cs/cθ for N =
20, q = 4, αb = 0.6 and different temperatures. Solid points (circles) and dashed lines indicate the position of the first order phase transition in the
cases τ/cθ = 2, 3, and 3.25.
αb ≥ αb,crit(cs) an increase in temperature triggers a jump-wise
collapse of the microgel. The critical value of αb,crit(cs) depends
nonmonotonously on salt concentration cs, that is, decreases at
low salt concentrations, passes through a minimum and then
increases at high salt concentrations. Hence, at fixed pH (fixed
αb) an increase in temperature provokes progressive deswelling
of the microgel particles either at small or at high salt
concentration, whereas discontinuous temperature-induced
volume transition can be expected in a certain range of
intermediate salt concentrations.
Remarkably, a decrease in N (equivalent to an increase in the
degree of cross-linking) leads to shrinkage of the region of
jump-wise collapse transition toward higher values of αb and to
a decrease in the magnitude of the jump in the size of the gel
particles. At given (buffered) value of pH, the range of salt
concentrations where discontinuous collapse may be observed
experimentally narrows upon a decrease in N and for strongly
cross-linked gel temperature-induced deswelling is expected to
occur smoothly at any salt concentration.
B. Salt-Induced Swelling-to-Collapse Transition. The
conformational response of the microgel particles to the
variation in the ionic strength of the solution at fixed
temperature and pH is more complex: The initial increase in
the salt concentration promotes ionization and, consequently,
provokes an increase in the osmotic pressure inside the gel. As a
result, swelling of the microgel particles occurs. As soon at the
degree of ionization of the microgel reaches (upon an increase
in salt concentration) its maximal possible value α ≈ αb, (at
given pH in the buffer) then a decrease in the differential
osmotic pressure caused by added salt governs deswelling of the
gel. As a result, the dependence of the size of the gel particles
on salt concentration acquires nonmonotonous character. A
similar effect has been predicted earlier for pH-sensitive
polyelectrolyte brushes30,31 and stars36 where stretching of
the brush-forming chains or of the star arms is governed by the
excess osmotic pressure exerted by entrapped counterions.
The dependence of the reduced size of the microgel particle
on salt concentration cs at different temperatures is presented in
Figure 3. As one can see from the Figure, under good solvent
conditions (T ≤ LCST) as well as in the vicinity of the Θ-point
(T ≈ LCST) the nonmonotonous but continuous variation in
the dimensions of the gel (swelling-contraction) occurs upon
an increase in salt concentration. On the contrary, under
moderately poor solvent conditions (T ≥ LCST) one or two
sharp conformational transitions accompanied by abrupt
changes in the dimensions of the microgel particles occur
upon progressive increase in salt concentration. As demon-
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strated by Figure 3a, a continuous increase in the microgel
particle size caused by addition of small amounts of salt can be
interrupted by a jump-wise swelling transition. Upon further
increase in salt concentration the gel shrinks. Depending on
temperature, this contraction either occurs continuously or
involves a jump-wise collapse transition.
As one can see in Figure 3b, the degree of ionization α of the
gel particles is a continuous and smoothly increasing function
of salt concentration under good or nearly Θ-solvent
conditions, T ≈ LCST, as well as under very poor solvent
conditions. Under moderately poor solvent conditions the
degree of ionization exhibits discontinuities which are coupled
to abrupt swelling and collapse of the gel particles upon an
increase in salt concentration. Moreover, in a narrow range of
temperatures, the degree of ionization exhibits a weak
maximum as a function of the ionic strength. These peculiarities
in the dependence of the degree of ionization of the gel
particles on salt concentration arise due to coupling between
ionization and local polymer density, that is expressed by eq 6.
The phase diagram of the microgel solution in (temperature,
salt concentration) coordinates is presented in Figure 4. The
Figure 4. Phase diagram of the microgel solution in the temperature−
salt concentration coordinates calculated for αb = 0.6 and different
degrees of cross-linking (the values of N indicated at the lines). The
lines are terminated by the critical points.
τtr(cs) lines in the Figure 4 correspond to the conditions of
coexistence between collapsed and swollen states for the
microgels with different degrees of cross-linking. Crossing of
the coexistence lines upon variation in temperature (at constant
ionic strength) or upon variation in the ionic strength (at
constant temperature) implies jump-wise transitions between
swollen and collapsed states of the microgel. Each of the first-
order transition lines ends in two critical points corresponding
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Macromolecules
Figure 5. Dependences of the reduced size of the microgel particles R/Rθ (a) and degree of ionization α (b) on the pH-controlled bulk degree of
ionization αb for N = 20, cs/cθ = 0.1 and different temperatures, as indicated at the curves. The dotted line in panel b corresponds to α = αb. Solid
points (circles) and dashed lines indicate the position of the pH-induced first order phase transition in the cases τ/cθ = 3 and 4.
to the lower and the upper critical salt concentrations. The
temperature-induced contraction of the gel particles occurs
continuously, without a jump in the size, if the salt
concentration in solution is kept below the lower or above
the upper critical salt concentration. The difference between
the former and the latter diminishes upon an increase in the
degree of cross-linking.
Remarkably, for weakly cross-linked microgels the depend-
ence of the transition temperature τtr on salt concentration cs is
a nonmonotonous function, that is, exhibits a maximum. The
presence of the maximum in the τtr(cs) dependence, Figure 4,
for weakly cross-linked microgels, indicates that in a certain
temperature range above LCST a progressive increase in the
salt concentration provokes two successive jump-wise con-
formational transitions in microgel particles: The first one
(which occurs at lower salt concentration) is the transition
from the collapsed weakly ionized state to the swollen strongly
ionized state, whereas the second one (which occurs at higher
salt concentration) is the transition from the swollen to the
collapsed state of the gel with concomitant drop in the degree
of ionization α. (For strongly cross-linked microgels the latter
transition is continuous).
C. pH-Induced Collapse-to-Swelling Transition. The
swelling of pH-sensitive microgel particles can be naturally
governed by changing pH of the solution that affects the degree
of ionization of the microgel particles. As follows from eq 6, the
degree of ionization α of the microgel increases/decreases
monotonously as a function of the bulk pH for anionic/cationic
gel. Importantly, at any pH in the buffer, α remains smaller than
αb which is directly related to the buffer pH by eq 7.
Figure 5b demonstrates that under good solvent conditions
(T ≤ LCST) the degree of ionization α in a swollen microgel
closely follows increasing αb, which is reflected in continuous
increase in the size of the gel particles, Figure 5a. The difference
between α and αb becomes more pronounced upon an increase
in temperature, particularly above LCST. The higher the
temperature, the larger the polymer concentration in the
microgel, the more significant is the deviation of α in the
collapsed (at small αb) gel from αb. On the contrary, the
difference between α and αb in the swollen gel is small at any
temperature at large αb.
The swelling of the microgel particles caused by an increase
in αb (governed by the pH) occurs smoothly at temperatures
below and around LCST (good, Θ, and marginal poor solvent
conditions). Upon an increase in temperature the pH-triggered
swelling transition becomes more sharp (occurs in a narrower
pH range). At high temperature (sufficiently above LCST) the
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pH-triggered transition from collapsed to swollen states occurs
with a jump in the gel size, as the first order phase transition
and it is accompanied by a concomitant jump-wise increase in
the degree of ionization α.
IV. DISCUSSION AND CONCLUSIONS
The presented above theory suggests that aqueous dispersions
of multiresponsive (pH- and thermoresponsive) microgels
exhibit a complex response to variations in temperature, ionic
strength of the solution and pH. Our conclusions are based on
the thermodynamic analysis of tunable balance between short-
range solvophilic/solvophobic interactions and excess osmotic
pressure exerted by the ions partitioned between the microgel
and the solution with the account of ionization equilibrium for
the monomer units of the gel-forming subchains. Assuming that
inside the microgel the charge of the ionized monomer units is
approximately compensated by excess concentration of mobile
counterions, we were able to derive analytical equation for the
degree of swelling of the microgel as a function of external
parameters (solvent strength, salt concentration, and pH in the
buffer).
Analysis of the temperature dependence of the degree of
swelling indicates that an increase in temperature (decrease in
the solvent strength) triggers the gel contraction. This
contraction occurs continuously at low and high ionic strength
whereas at intermediate salt concentration a jump-wise
temperature-induced shrinkage of the microgel particles is
expected. The range of salt concentration corresponding to the
discontinuous temperature-induced collapse of the gel becomes
wider upon a decrease in the degree of cross-linking (an
increase in N).
Furthermore, similarly to pH-sensitive polyelectrolyte
brushes30,31 or star-branched polyelectrolytes,35,36 the microgel
particles are expected to exhibit nonmonotonous dependence
of their dimensions on salt concentration: an increase in the
microgel size at low ionic strength is followed by a decrease at
high ionic strength. The appearance of a maximum in the
particle size dependence on salt concentration is explained by
the fact that the ionization inside the microgel is suppressed at
low ionic strength but grows upon moderate increase in salt
concentration. The theory-predicted variation of the microgel
particle size as a function of salt concentration is smooth under
good, Θ, or marginal poor solvent conditions (below or around
LCST), whereas under moderately poor solvent conditions
(above LCST) successive swelling and collapse of the microgel
may occur as a jump-wise first-order phase transition.
dx.doi.org/10.1021/ma401402e | Macromolecules 2013, 46, 8702−8709
Macromolecules
The universality of predictions of our theory concerning
complex behavior of the microgel upon variation in temper-
ature or/and salt concentration and character of the stimuli-
induced volume transitions is assured by the account of only
main thermodynamic forces (contributions to the free energy)
acting in the system. Additionally, ion binding to the chains,
variation in local dielectric constant upon gel collapse, etc., may
influence quantitatively the shape of the swelling curves.
However, corresponding analysis requires application of more
sophisticated numerical schemes for the free energy mini-
mization60 and involves unavoidably empirical adjustable
parameters. At the same time, phenomenology of any particular
experimental system can be even richer due to polymer- or ion-
specific effects possibly coming into play. For example, similarly
to polyelectrolyte brushes and stars, reswelling of cationic
hydrogels collapsed at moderate salt concentration may occur
at very high ionic strength (more than one mol per liter) if I− or
Br− are used as counterions.61,62 This behavior was explained
theoretically using modified Donnan theory in terms of volume
of the ions in ref 63, but it is not related to the pH-sensitive
properties of the gel, i.e., could be expected for strong
polyelectrolyte gels as well. The comprehensive analysis of such
ion-specific effects is, however, beyond capabilities of the mean-
field theoretical approaches.
Furthermore, in the present study we focused only on the
influence of monovalent salt on the swelling of the microgels. It
is known that multivalent counterions provoke much stronger
collapse of polyelectrolyte brushes or branched polyelectrolytes
as compared to that induced by monovalent salt ions.3,49−52
Similar effects of the ion valence should be expected for
microgels as well and can be qualitatively explained by
preferential localization and lower osmotic pressure exerted
by multivalent ions inside polyelectrolyte brushes or stars (or,
equally, in microgels). At the same time, in the case of
multivalent counterions quantitative analysis points to the
importance of ion−ion or/and ion−polymer correlations,
which leads to stronger collapse as compared to prediction of
the theory based on the osmotic balance arguments.50,52 A
quantitative analysis of the ion−ion correlations in strongly
charged polyelectrolyte gels based on the liquid-state integral
equation theory has been presented in the recent work.53 The
contribution of ion−ion correlations to swelling of polyelec-
trolyte brushes54 or gels is, however, negligible in the case of
monovalent ions considered here.
At this point it is worth mentioning that a possibility of
discontinuous collapse transitions provoked by decreasing
solvent strength has been suggested earlier for star-branched
polyelectrolytes and polyelectrolyte brushes on the basis of
theories which exploited box-like models.54−57 More accurate
analysis with the account of nonuniform distribution of
polymer density and nonequal stretching of chains in
polyelectrolyte stars or in brushes proved that under poor
solvent conditions coexistence of swollen and collapsed
conformations occurs in polyelectrolyte stars or brushes on
the level of individual chains.58,59 More specifically, a decrease
in the solvent strength or/and an increase in salt concentration
provokes microphase segregation in a star (or in a brush). This
segregation is manifested in the formation of dense central
region formed by less extended chains and sparse outer region
formed by more extended chains. In the case of pH-sensitive
polyelectrolytes the degree of ionization of the chains in the
dense phase is smaller than that of the chain forming the
extended phase.23,39,40 The variation of temperature or/and salt
8708
Article
concentration results in progressive repartitioning of the chains
between the two phases and concomitant smooth variation of
the experimentally measurable dimensions of the stars or
brushes. On the contrary, under the same conditions the cross-
linked pH- and thermoresponsive microgel particles are
expected to exhibit discontinuous volume transitions man-
ifested in abrupt variation in the particles dimensions and in
coexistence of collapsed and swollen microgel particles in
solution in the vicinity of the transition point.
Finally, we remark that an interplay of short-range
monomer−monomer attraction with long-range Coulomb
repulsion may result (at low ion concentration inside the gel)
in formation of nanoscale collapsed hydrophobic domains
along subchains,64 association of subchains into bundles,65,66 or
other types of the domain structures.67,68 As has been discussed
in ref 66, because of branched topology, multiple morphologies
of microdomain structures may appear in partially collapsed
hydrophobic polyions. The formation of locally collapsed
hydrophobic domains may lead to smoothening of abrupt first-
order volume transitions in hydrogels. A more refined analysis
of these effects based on Monte Carlo or molecular dynamics
simulations is necessary.
The predictions of our theory can be checked, e.g., by
dynamic light scattering or viscosimetry in dilute aqueous
dispersion of multiresponsive microgels. Indeed, the aqueous
dispersions of the microgels often convey colloidal stability (or
exhibit very slow coagulation) even in the collapsed state due to
residual charges of the particles. In addition, the particle
concentration can be low, while still allowing efficient light
scattering.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: oleg.borisov@univ-pau.fr.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work has been partially supported by the Russian
Foundation for Basic Research (Grant 11-03-00969a), by
Department of Chemistry and Material Science of the Russian
Academy of Sciences, and by German Research Foundation
(DFG) within SFB 985.
■
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