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Ionic effects on synthetic polymers: from

solutions to brushes and gels
Cite this: Soft Matter, 2020,
16, 4087
Haiyang Yuan and Guangming Liu *

Received 4th February 2020,
Accepted 3rd April 2020
DOI: 10.1039/d0sm00199f
rsc.li/soft-matter-journal
The ionic effects on synthetic polymers have attracted extensive attention due to the crucial role of ions
in the determination of the properties of synthetic polymers. This review places the focus on specific ion
effects, multivalent ion effects, and ionic hydrophilicity/hydrophobicity effects in synthetic polymer
systems from solutions to brushes and gels. The specific ion effects on neutral polymers are determined
by both the direct and indirect specific ion–polymer interactions, whereas the ion specificities of
charged polymers are mainly dominated by the specific ion-pairing interactions. The ionic cross-linking
effect exerted by the multivalent ions is widely used to tune the properties of polyelectrolytes, while the
reentrant behavior of polyelectrolytes in the presence of multivalent ions still remains poorly
understood. The ionic hydrophilicity/hydrophobicity effects not only can be applied to make strong
polyelectrolytes thermosensitive, but also can be used to prepare polymeric nano-objects and to
control the wettability of polyelectrolyte brush-modified surfaces. The not well-studied ionic hydrogen
bond effects are also discussed in the last section of this review.

1. Introduction particles.4–8 It has been widely recognized that the ion-related

Ions are widely dispersed in natural environments such as
seawater, soil, and biological systems.1–3 In analogy to the
natural environments, ions are also extensively used in a wide
range of artificial systems, e.g., synthetic polymers and colloidal
Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory
of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education
Institutes, Department of Chemical Physics, University of Science and Technology of
China, No. 96, Jinzhai Road, Hefei 230026, P. R. China. E-mail: gml@ustc.edu.cn
interactions play an important role in the determination of the
properties of many natural and artificial systems.2,9,10 According
to the classical Debye–Hückel (DH) theory, the ion-related inter-
actions in electrolyte solutions are dominated by the electrostatic
interactions mediated by the ionic strength.11 This subclass
of ionic effect can be defined as the ionic strength effect.10
However, the assumptions involved in the DH theory have
limited its applications for understanding many important ionic
effects in electrolyte solutions beyond the ionic strength
effect.4,9,10,12–15 For example, the DH theory assumes that the

Haiyang Yuan received his BS Guangming Liu received his BS

degree from Anhui Normal Univer- degree from Anhui Normal Univer-
sity in 2017. He is currently sity in 2002 and his PhD degree
pursuing his PhD degree at the from University of Science and
Department of Chemical Physics Technology of China in 2007. He
at University of Science and worked as a research assistant at
Technology of China. His present The Hong Kong University of
research interests focus on the Science and Technology from
ionic effects on synthetic polymers. 2005 to 2006 and worked as a
postdoctoral fellow at The
Australian National University
from 2008 to 2010. He is
Haiyang Yuan Guangming Liu currently a professor at Univer-
sity of Science and Technology of
China. His present research interests focus on the ionic effects in
macromolecular systems from fundamentals to applications.

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ions are nonpolarizable and electrolytes completely dissociate
into ions in solutions (i.e., no ion pairs are formed).11 This means
that the DH theory does not consider the wildly recognized
specific ion effects in electrolyte solutions.2 Therefore, the detailed
discussions on the ionic effects beyond the ionic strength effect
are significant for understanding of the ion-related interactions in
various systems.
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For the synthetic polymers, the ionic effects including
specific ion effects, multivalent ion effects, and ionic hydro-
philicity/hydrophobicity effects have been extensively studied
during the past few decades, but the exact mechanisms of
relevant ionic effects are still under debating.4,9,10,16–25 Herein,
instead of giving an extensive review of the above-mentioned
three subclasses of ionic effects in all the synthetic polymer
systems, we plan to choose polymer solutions, brushes, and
gels as the typical polymer systems to exemplify the ionic effects
on synthetic polymers. As the polymer structure, concentration,
and composition can be easily controlled in solutions, the
discussions on the ionic effects in polymer solutions will be
important for understanding of the fundamentals of ionic
effects on synthetic polymers. Polymer brushes not only can
be employed to understand the fundamental aspects of ionic
effects, but also can be used to demonstrate the applications of
ionic effects to tune the polymer properties. Considering that
polymer gels are one type of the most important polymeric
materials,13,21,26–28 the discussions regarding the ionic effects
on polymer gels will greatly demonstrate the availability for the
use of ionic effects to control the performance of polymeric
materials.
Over the past ten years, several excellent reviews have been
published from other research groups to understand the ionic
effects on synthetic polymers.24,29–31 Each of these previous
reviews has only focused on one subclass of the ionic effects on
polymers.24,29–31 An overview of the specific ion effects in
thermoresponsive polymer solutions30 and a comparison of
the specific ion effects on thermosensitive polymer brushes
with those on the polymers with other architectures29 were
provided in recent reviews to understand the mechanism of
ion specificities of polymers. For the multivalent ion effects,
Ballauff et al. have reviewed the behavior of polyelectrolytes in
the presence of multivalent ions in aqueous solutions to stress
that the conformation and interaction of star polyelectrolytes
and spherical polyelectrolyte brushes can be tuned by multi-
valent ions.31 For the ionic hydrophilicity/hydrophobicity effects,
the importance of the hydrophilic/hydrophobic properties of
counterions in the determination of the thermosensitivity of
poly(ionic liquids) was discussed in a recent review.24 In compar-
ison with these previous reviews, we herein will systematically
discuss the three subclasses of extensively studied ionic effects in
three types of typical polymer systems. The not well-studied ionic
hydrogen bond effects are also discussed in this review. Thus, our
review will not only detailedly discuss the current understanding
of each subclass of ionic effects in different polymer systems, but
also provide an opportunity to compare the different ionic effects
for the same polymer system. This is important because the
different ionic effects could coexist in one polymer system and
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the interplay between the different ionic effects would have a
strong influence on the properties of polymers. Therefore, we
anticipate that the current review presented here will provide a
great understanding of the ionic effects on synthetic polymers
from fundamentals to applications.
2. Specific ion effects
The specific ion effects were first observed in 1888, when the
Czech scientist Franz Hofmeister defined both anion and
cation trends according to the ionic capabilities to affect the
protein solubility in aqueous solutions.32 Besides the proteins,
the specific ion effects have also been observed in other systems
of naturally occurring macromolecules such as polypeptides
and DNA.2,33–37 Analogous to the natural macromolecules, the
properties of both neutral and charged synthetic polymers are
also strongly dependent on the nature of ions presented in the
polymer systems.4,9,10,22,38–43 In the following subsections, the
specific ion effects on neutral and charged synthetic polymers
will be separately discussed for polymer solutions, brushes,
and gels.
2.1 Specific ion effects in polymer solutions
2.1.1 Neutral polymer solutions. Numerous investigations
have been performed to explore the specific ion effects in
neutral polymer solutions.4,9,19,30,44–46 It has been reported that
the direct ion–polymer interactions and the indirect water-
mediated ion–polymer interactions are the two main factors to
determine the specific ion effects in neutral polymer solutions.4,9
Cremer et al. have systematically studied the specific ion effects
on a typical neutral polymer, poly(N-isopropylacrylamide)
(PNIPAM), in aqueous solutions.4,38 A model consisting of three
kinds of interactions between anions, PNIPAM, and water mole-
cules has been suggested to explain the observed specific ion
effects on the solubility of PNIPAM in aqueous solutions.4 More
specifically, a salting-out effect is caused by either the destabiliza-
tion of hydrogen bonding between PNIPAM and water molecules
via an anionic polarization or an increase in the PNIPAM/water
interfacial tension with increasing salt concentration, whereas a
salting-in effect is caused by a direct binding of chaotropic anions
to the PNIPAM surface.4 Such a model can be used to understand
the ion specificities of other types of neutral polymers as well,
such as poly(2-ethyl-2-oxazoline),47 poly(N,N-diethylacrylamide),48
and poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene
oxide) block copolymer.19,44
In general, the specific ion effects in polymer solutions are
dominated by the ion–polymer interactions. For instance, a
direct binding of the chaotropic I to PNIPAM surface can
result in a salting-in effect, whereas a salting-out effect can be
caused by a destabilization of hydrogen bonding between
PNIPAM and water molecules through an anionic polarization
by the kosmotropic SO42.4 Nevertheless, the specific ion effects
in polymer solutions could also be influenced by the coexisted
salts via modulating the ion–polymer interactions.49 As many
complex environments such as seawater and biological systems
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Fig. 1 Schematic illustration of the mechanism of specific interactions
between anions and PNIPAM in mixed salt solutions. The curved arrow
represents the partitioning of Na+ from I to SO42, leaving I more
hydrated, and thereby leading to a collapse of PNIPAM. On the other
hand, the salting-out effect generated by SO42 causes to a stronger
binding of I to the polymer/water interface, resulting in a swelling of
PNIPAM. Reproduced with permission from ref. 50. Copyright 2019
American Chemical Society.
contain many types of ions simultaneously,1,2 the studies on ion
specificities of polymers in salt mixtures are highly important for
understanding of the mechanism of specific ion effects in
complex environments. van der Vegt et al. have recently investi-
gated the thermoresponsive phase behavior of PNIPAM in a
mixture of two salts with the common cation Na+ but very
different counter anions of the weakly hydrated I and the
strongly hydrated SO42 (Fig. 1).50 The SO42 can either lead to
a preferential partitioning of Na+ to its counterion cloud, leaving
I more hydrated than that in a corresponding pure salt solution,
giving rise to a collapse of polymer due to the salting-out effect, or
salt out the I to the polymer/water interface, resulting in a
swelling of the polymer induced by the direct binding of I to
polymer surface.50 Therefore, the specific ion effects on the
thermosensitive behavior of PNIPAM in the mixed salt solutions
are influenced by a subtle balance between the two opposite
effects discussed above.50
Considering that the ion specificities of polymers in aqueous
solutions are closely correlated with the water-mediated indirect
ion–polymer interactions, the addition of organic solvents to
water would strongly affect the ion specificities due to the
interactions between water and organic solvents. The extension
of studies on ion specificities of polymers from water to organic
solvents is important for understanding of the mechanism and
for improving the performance of energy storage systems.51
We have performed systematic investigations on the ion speci-
ficities of thermosensitive polymers in water–organic solvent
mixtures.22,40,52–54 It is found that the relative strength of
specific ion effects on the lower critical solution temperature
(LCST) behavior of PNIPAM can be amplified by the addition of
methanol.52 This is because the water/methanol complexes are
able to differentiate the different types of ions through the ion-
modulated shift of the equilibrium between solvent complexes
and free solvent molecules, triggered by the specific ion-solvent
complex interactions.52 As the water/methanol complexes are a
poorer solvent for PNIPAM compared with pure water or
methanol,55,56 the specific ion effects on the LCST of PNIPAM
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are expected to be amplified by the addition of methanol owing
to the fact that more water/methanol complexes are formed
upon the addition of methanol to water in a certain range
of solvent composition.52,55,56 Moreover, the amplification of
specific ion effects is also influenced by the chemical structures
of alcohols as the stability of water/alcohol complexes is related
to the chemical structures of alcohols.53 A more stable solvent
complex can more effectively differentiate the different types of
ions through the specific ion–solvent complex interactions,
thereby leading to a stronger amplification of specific ion
effects on the LCST of PNIPAM.53
In comparison with the alcohols which are protic organic
solvents with both hydrogen bond donors and acceptors, the
aprotic organic solvents can only act as the hydrogen bond
acceptors. Consequently, the addition of aprotic organic
solvents, e.g., dimethylsulfoxide (DMSO), gives rise to very
different specific ion effects from those for the protic organic
solvents.22,54 An inverted V-shaped anion series is observed in
terms of the anion-specific upper critical solution temperature
(UCST) of PNIPAM in a DMSO–H2O mixture at a molar fraction
of DMSO of 70%.22 Nevertheless, a question remains to be
answered. That is, does the ion specificity of thermosensitve
polymers exist in a pure aprotic organic solvent? This question
is difficult to be answered with the PNIPAM system, because
PNIPAM is usually temperature insensitive in pure aprotic
organic solvents (e.g., DMSO and acetone).57,58 To answer this
question, we have employed a polymer-supported borinic acid
(PBA) as an effective model system to investigate the ion
specificity of thermosensitve polymers in DMSO.54 Fig. 2 shows
that the added anions can either directly interact with the
partially positively charged boron atom of PBA, or indirectly
interact with PBA through the anionic polarization of hydrogen
bonding between PBA and DMSO molecules.54 Both of these
two types of interactions can generate a salting-in effect on the
solubility of PBA in DMSO.54 The combination of direct and
indirect anion–PBA interactions leads to an inverted V-shaped
series CH3COO o Cl o salt-free 4 NO3 4 ClO4 4 SCN
in terms of the anion-specific UCST of PBA in DMSO.54
2.1.2 Charged polymer solutions. When ions are presented
in charged polymer solutions, the counterions can specifically
interact with the charged groups associated with polymers,
which would lead to obvious specific ion effects. The specific
ion pairing interactions between counterions and the charged
groups can be understood on the basis of the law of matching
water affinities (LMWA).59,60 According to the LMWA, strongly
(weakly) hydrated counterions can form contact ion pairs with
the strongly (weakly) hydrated charged groups of the polymers,
whereas the ion pairing interactions are weak for the counterions
and charged groups with mismatched hydration strengths.59,60
The LMWA can well explain the ion specificities of poly-
electrolytes in aqueous solutions and can be extended to under-
stand the specific ion effects in nonaqueous solvents.61–63 It
should be noted that the specific interactions between counter-
ions and the charged groups of polyelectrolytes can also be
understood by the theory of ion dispersion forces, though the
prediction by the theory of ion dispersion forces appears to be
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Fig. 2 Schematic illustration of the specific interactions between anions
and PBA in DMSO. The anions can either directly bind to PBA surface or
indirectly interact with PBA through the anionic polarization of hydrogen
bonding between PBA and DMSO molecules. Reproduced with permission
from ref. 54. Copyright 2018 American Chemical Society.
conflicted with that derived from the LMWA in some specific
cases.64
Based on the specific interactions between counterions and
the charged groups of polymers, the ion identity can be used
to modulate the properties of charged polymers in solutions.
Our group has demonstrated that the fluorescence properties of
both positively and negatively charged star polyelectrolytes can
be tuned by counterion identity through the specific ion pairing
interactions.65 The studies from other research groups have
shown that the ion identity can be applied to modulate the
micellization of positively charged ammonium-containing
block copolymers,66 the thermosensitive behavior of a
negatively charged copolymer,67 and the polyelectrolyte com-
plexation in aqueous solutions.68 In comparison with polyelec-
trolytes, the specific ion effects on the solution behavior of
polyzwitterions are more complicated and require further stu-
dies to clarify the relevant mechanisms.69
2.2 Specific ion effects on polymer brushes
2.2.1 Neutral polymer brushes. It is known that the proper-
ties of polymers are dependent on their architectures, for
example, the confined architecture of polymer brushes endow
them many unique properties compared with the free polymer
chains in solutions.70 Nevertheless, the influence of confined
architecture on the ion specificities of polymers is still not well
understood.29 Several works about the specific ion effects on
neutral polymer brushes have recently been published.71–75
Webber et al. have investigated the specific ion effects on
the thermosensitive behavior of PNIPAM brush-grafted silica
colloidal particles and have shown that the ion identity can
be applied to control the electrophoretic mobility of the
particles.73 By the use of dynamic light scattering and atomic
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force microscopy, the same research group has investigated the
stability of PNIPAM brush-grafted silica colloidal particles and
the interactions between PNIPAM brushes in the presence of
different types of anions.74 The specific ion effects on the
stability of particles can be understood by considering both
the specific ion binding and the electrostatic Debye screening
length.74 For example, the increased charging of the PNIPAM
brush due to the binding of SCN at a low salt concentration
effectively extends the range of the electrostatic repulsion to
outside of the collapsed brush layer, leading to a stabilization
of the particles at high temperatures.74
Wanless et al. have systematically studied the specific ion
effects on the thermoresponsive behavior of poly(di(ethylene-
glycol) methyl ether methacrylate) (PMEO2MA) brushes and
have found that the SCN exhibits a stronger effect on the
PMEO2MA brushes than the PNIPAM brushes with similar
thickness and grafting density in terms of its influence on
thermosensitivity of the brushes.71 Recently, they have also
investigated the specific ion effects on the thermoresponsive
behavior of statistical copolymer brushes, poly(di(ethylene-
glycol) methyl ether methacrylate)-stat-poly[(oligo(ethylene glycol)
methyl ether methacrylate]) (P(MEO2MA-stat-OEGMA300))
brushes, in the salt mixtures of CH3COOK and KSCN.75 It is
shown that the ion-specific effects between CH3COO and
SCN on the copolymer brushes are offset each other at low
temperatures, and the specific anion effects on the copolymer
brushes are weakened and relatively strengthened for
CH3COO and SCN, respectively, at high temperatures.75 This
is because the collapse of the brushes at high temperatures
limits the penetration of the CH3COO ions into the brushes
due to both the increased steric chain crowding in the brushes
and the large hydration number of the CH3COO ion.75 In
addition, the specific ion effects on the thermosensitivity of
P(MEO2MA-stat-OEGMA300) brushes are also dependent on the
copolymer composition.72
2.2.2 Charged polymer brushes. It is well-known that poly-
electrolyte brushes can be classified into strong polyelectrolyte
brushes (SPBs) and weak polyelectrolyte brushes (WPBs).15 It is
generally thought that the charge density of the former is
independent of pH, whereas the degree of charging of the later
can be controlled by pH due to the pH-mediated proton
dissociation–association of acidic or basic groups.10,15,76,77
For the SPBs, it has been demonstrated that the counterion
identity plays an important role in the determination of the
properties of the brushes.9,10 Our group has investigated the
specific anion effects on the properties of the positively charged
poly[2-(methacryloyloxy)ethyltrimethylammonium chloride]
(PMETAC) brushes and has demonstrated that the specific
anion effects are dominated by the indirect anion-specific
competition for water molecules and the direct specific ion-
pairing interactions for kosmotropic and chaotropic anions,
respectively.78 The two different manners of interactions give
rise to a V-shaped anion series in terms of the anion-specific
hydration of the PMETAC brushes.78 We have recently also
shown that the specific anion effects on the PMETAC brushes
can be observed even at very low salt concentrations induced by
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the specific ion-pairing interactions.79 Specifically, the PMETAC
brushes dehydrate and collapse upon the introduction of a low
concentration of ClO4 counterions due to a stronger interaction
of the quaternary ammonium group with ClO4 compared with
that with Cl, whereas the hydration of the PMETAC brushes is
increased accompanied by a swelling of the brushes with the
addition of CH3COO counterions owing to a weaker interaction
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of the quaternary ammonium group with CH3COO than that
with Cl.79 Takahara et al. have found that a more chaotropic
counterion can more strongly bind to the weakly hydrated charged
group of the SPBs, causing the SPBs to dehydrate and collapse
more strongly with a lower zeta potential.80 It is worth noting
that the specific ion effects on the swelling and collapse of SPBs
can also be observed in organic solvents.51 Due to the different
polarizabilities of different organic solvents, the ion trends
observed in methanol and formamide are reversed compared with
those observed in DMSO and propylene carbonate.51
The pH response of WPBs originates from the pH-mediated
degree of charging of grafted weak polyelectrolyte chains.10,76
Therefore, the strength of pH response of WPBs should be
controlled by the counterion identity if the charge state of
WPBs can be tuned by the specific ion-pairing interactions
between counterions and the charged groups of the grafted
chains (Fig. 3).81 As shown in Fig. 3, both pH and counterion
identity can be used to modulate the degree of charging of the
grafted positively charged weak polyelectrolyte chains through the
association–disassociation of protons with the dimethylamino
Fig. 3 Schematic illustration of the tuning of pH response of WPBs with specific anion effects. Reproduced with permission from ref. 81. Copyright 2018
American Chemical Society.
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groups and the specific ion-pairing interactions between counter-
ions and the protonated dimethylamino groups, respectively.81
A more strongly chaotropic anion can more effectively reduce
the extent of charging of the grafted chains through a stronger
ion-pairing interaction with the weakly hydrated protonated
dimethylamino group, giving rise to a weaker strength of pH
response of the WPBs.81
As the conformation of polyelectrolytes is dependent on
the electrostatic interactions between the charged groups asso-
ciated with the polymer chains, the counterion identity can be
applied to adjust the conformation of WPBs through the
counterion-specific screening of the electrostatic interactions.82,83
For the cationic WPBs, the addition of chaotropic SCN gives
rise to a more collapsed conformation of the brushes due to a
stronger electrostatic screening generated by a higher affinity of
the SCN ions, whereas the addition of Ac results in a relatively
extended conformation of the brushes owing to a weaker
electrostatic screening induced by a lower affinity of the Ac
ions.82,83 Due to the specific interactions between counterions
and cationic WPBs, an interesting ion-specific swelling behavior
of the WPBs is observed in salt mixtures.84 The swelling of
cationic WPBs in the mixtures of NO3 and Cl is simply the
linear combination of the swelling behavior in corresponding
single salt solutions, whereas the swelling of cationic WPBs in
the mixtures of SCN and Cl considerably deviates from the
average behavior due to a stronger interaction of the brushes
with SCN than that with Cl.84
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In contrast to polyelectrolyte brushes, polyzwitterionic brushes
usually adopt a more collapsed conformation with a weaker
hydration at low salt concentrations due to the inter-/intrachain
dipole–dipole interactions, but adopt a more extended conforma-
tion with a stronger hydration at high salt concentrations
attributed to the weakened dipole–dipole interactions.85 As the
different types of anions can specifically interact with the posi-
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tively charged quaternary ammonium of the zwitterionic group,
the hydration and conformation of the polyzwitterionic brushes
can be readily tuned by the anion identity.23 According to the
LMWA, the interaction between anions and the quaternary
ammonium group becomes stronger following the anion trend
SO42 o Cl o Br o ClO3 o SCN o ClO4.59 That is, a more
chaotropic anion can more effectively weaken the inter-/intra-
chain dipole–dipole interactions. Consequently, a higher extent of
hydration of the polyzwitterionic brushes is resulted as the
identity of presented anions changes from SO42 to ClO4 along
the anion trend. The specific anion effects on the polyzwitterionic
brushes are also dependent on the carbon spacer length between
the positively and negatively charged groups, as both the inter-/
intrachain associations and the formation of cyclic intramolecular
structures are correlated with the carbon spacer length.12
As discussed above, the hydration and conformation of
SPBs, WPBs, and polyzwitterionic brushes can be controlled
with specific ion effects. Considering that many important
properties of charged polymer brushes are determined by their
hydration and conformation, it is expected that these proper-
ties can be tuned with specific ion effects as well. It has been
demonstrated that the properties of SPBs including swelling,
stiffness, wettability, and lubrication can be controlled by the
counterion identity through the specific interactions between
counterions and the charged groups of the grafted chains.86–88
Besides, the counterion identity can also be applied to tune the
release rates of killed bacteria from the surface of SPBs,89 the
adsorption of protein on the surface of SPBs,90 and the ice
nucleation and propagation on the surface of SPBs.91,92 More-
over, a recent study has shown that the charge inversion
induced by an over-adsorption of chaotropic anions can cause
to a current rectification inversion of the SPBs-modified
nanopipettes.93 In analogy to SPBs, specific ion effects can also
be used to tune the surface adhesion and wettability of
WPBs81,94 and to control the protein adsorption, wettability,
and friction coefficients of polyzwitterionic brushes.12,23,95
2.3 Specific ion effects on polymer gels
2.3.1 Neutral polymer gels. In comparison with neutral
polymer solutions, fewer studies have been performed to
investigate the ion specificities of neutral polymer gels. Liu et al.
have demonstrated that the critical gelation temperature (CGT) of
thermosensitive polymer gels decreases with increasing concen-
tration of Na2CO3 because a denser and tighter association of
polymer segments is resulted in the presence of a higher concen-
tration of kosmotropic CO32 ions.96 Meanwhile, the strengthened
polymer network gives rise to a higher storage modulus (Ggel0 ) at a
higher Na2CO3 concentration.96 Kouwer et al. have also shown that
specific anion effects can be used to tune both the temperature of
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gelation and the mechanical properties of the ethylene glycol-
functionalized polyisocyanides gels by modulating the interactions
between polymer and water.97 As a result, the stiff and soft gels
can be obtained in the presence of kosmotropic and chaotropic
anions, respectively.97 Likewise, the properties of other polymer
gels including the thermogelling behavior of poly(organo-
phosphazenes),98 the reentrant behavior of PNIPAM microgels,99
the translational viscosity and solvation dynamics in a PEO–PPO–
PEO hydrogel,100 and the volume transition temperature of
PNIPAM gels101,102 can be tuned with specific ion effects as well.
The tuning of the properties of neutral polymer gels with specific
ion effects can be well understood based on the same underlying
mechanisms discussed in the subsections of polymer solutions
and brushes.
2.3.2 Charged polymer gels. By the utilization of
counterion-specific binding affinity with the positively charged
quaternary ammonium group, a dynamic hydrophobicity gradient
within a charged polymer hydrogel can be formed via a counterion
exchange strategy.103 It is found that the bis(trifluoromethane)-
sulfonimide (TFSI) triggered gradient in the poly([2-(methacryloy-
loxy)ethyl] trimethylammonium chloride) (PMTACl) hydrogel
propagates faster than that in the PMTASCN hydrogel.103 This
is because the rate of counterion exchange between Cl and
TFSI is faster than that between SCN and TFSI due to the
more hydrophilic character of Cl compared with SCN.103 The
developed dynamic gradient is able to direct molecular transport
and concentration in the hydrogel films.103 Based on the specific
ion-pairing interactions between counterions and the charged
groups of polymers, specific ion effects can be employed to tune
the properties of hydrogels containing both positively and
negatively charged groups.104,105 Chung et al. have applied
specific ion effects to control the ionic conductivity and mechan-
ical strength of polyampholyte hydrogels through the dialysis of
the hydrogels in different types of electrolyte solutions.105 The
ion-tunable polyampholyte hydrogels have potential applications
as gel polymer electrolytes in the field of electrochemical energy
storage devices.105 When positively and negatively charged poly-
electrolytes are mixed together to form the polyion complex
hydrogel, the mechanical properties and self-healing efficiency
of the hydrogel can be easily controlled with specific ion effects
through ion-specific breaking of the ionic bonds formed within
the hydrogel.104
To further demonstrate the tuning of the properties of
charged polymer gels with specific ion effects, we have recently
applied the anion identity to control the photoresponse of a
zwitterionic azobenzene (Azo)-containing polymer hydrogel
(Fig. 4a).106 The rate of dynamic wagging (Rw) of the Azo groups
increases following an anion trend Cl o NO3 o ClO3 o Br
during the gel-to-sol transition under irradiation with the
combination of ultraviolet and visible (UV + Vis) light (Fig. 4b).106
A more chaotropic anion can more effectively weaken the dipole–
dipole interactions between the zwitterionic groups, leading to a
lower energy barrier for the dynamic wagging of the Azo groups.
This is why a higher Rw is obtained in the presence of a more
chaotropic anion.106 Moreover, the weaker dipole–dipole inter-
actions induced by the more chaotropic anion would promote
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Fig. 4 (a) Schematic illustration of the cooperative action between the different components of sunlight to facilitate the gel-to-sol transition. UV and Vis
light can be converted into mechanical energy simultaneously to synergistically power the dynamic wagging of the Azo groups, while the infrared (IR)
light can be converted into kinetic energy of the zwitterionic groups to promote the dynamic wagging of the Azo groups. (b) Rw of the Azo groups under
irradiation with UV + Vis light in the presence of different anions with Na+ as the common cation. (c) tg–s of the hydrogel under irradiation with UV + Vis
light in the presence of different anions with Na+ as the common cation. Adapted with permission from ref. 106. Copyright 2019 American Chemical
Society.

the gel-to-sol transition, leading the time required to realize the
gel-to-sol transition (tg–s) to decrease following an anion trend
Cl 4 NO3 4 ClO3 4 Br under irradiation with UV + Vis
light (Fig. 4c).106 On the other hand, according to the LMWA, the
weakly hydrated positively charged alkyl quaternary ammonium
group has a strong ion-pairing interaction with the weakly
hydrated negatively charged alkyl sulfonate group,59,107 thus, it
is expected that the poly(sulfobetaine methacrylamide) will be an
attractive candidate to be developed as a zwitterionic gel polymer
electrolyte for solid-state supercapacitors.28,108
3. Multivalent ion effects
3.1 Multivalent ion effects in polymer solutions
For the multivalent ion effects, we here only focus on the
polyelectrolyte systems, though the multivalent ions can also
interact with neutral polymers through the chelation inter-
actions.31,109,110 The most straightforward effect generated by
the multivalent ions in polyelectrolyte solutions should be the
ionic cross-linking effect. The previous work performed by Peng
and Wu has shown that the self-complexation of partially
hydrolyzed poly(acrylamide) (HPAM) chains in the presence of
Ca2+ changes from intrachain to interchain complexation with
increasing concentration of Ca2+ ([Ca2+]).111 At a lower ratio of
[Ca2+] to the concentration of carboxylate group ([Ca2+]/
[–COO]), the intrachain cross-linking by Ca2+ leads to a
collapse of the HPAM chains. At a higher ratio of [Ca2+]/
[–COO], the interchain cross-linking by Ca2+ gives rise to the
formation of large polyelectrolyte aggregates. Likewise, the
anionic divalent SO42 ions can be used to induce the micelli-
zation of poly(ethylene glycol)-block-poly(4-vinylpyridinium)
(PEG-b-P(4-VPH+)) in aqueous solutions via the ionic cross-
linking effect.112 As the cross-linking effect of multivalent ions
is dependent on ion valency, Ballauff et al. have employed UV
light to adjust the valency of multivalent ions to manipulate the
conformation of polyelectrolyte stars.113 Under the irradiation
with UV light, the trivalent hexacyanocobaltate(III) ([Co(CN)6]3)
counterions are transformed into a mixture of divalent
aquapentacyanocobaltate(III) ([Co(CN)5H2O]2) and monovalent
cyanide (CN) ions. In doing so, the collapsed conformation
of cationic polyelectrolyte stars in the presence of [Co(CN)6]3
can be reopened by the UV light.113 With the same strategy,
the photosensitive [Co(CN)6]3 ions can also be applied to
control the UCST behavior of a weak polyelectrolyte in aqueous
solutions.114

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There is an open question remained for polyelectrolytes in
the presence of multivalent ions. That is, what is the precise
cause of the re-expansion or re-dissolution of polyelectrolytes
in the high concentration regime of multivalent ions? As the
concentration of multivalent ions increases, the expanded
conformation of polyelectrolyte chains collapses into a compact
structure, which may lead to a phase separation of polyelec-
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trolyte solutions and a precipitation of polyelectrolytes.115,116
The collapsed polyelectrolyte chains re-expand with a further
increase in the concentration of multivalent ions.115,116 This
reentrant behavior is usually ascribed to the charge inversion of
polyelectrolytes induced by the multivalent ions.117–120 On a
charged surface, a strongly correlated liquid layer formed by
multivalent counterions could generate an attraction to the
counterions, resulting in overcharging at the surface.121–123 For
polyelectrolytes, the correlation-induced short-range attraction
(like charge attraction) would lead to a condensation of poly-
electrolytes, where the surface charge of polyelectrolytes is
almost completely compensated by the condensed multivalent
counterions.117,124 As the concentration of multivalent ions
increases further, the charge inversion of polyelectrolytes increases
the Coulomb repulsions between polyelectrolyte chains, causing to
a dissolution of the condensed polyelectrolytes.117,124
Theoretically, a phase diagram has been proposed to illus-
trate the transition of polyelectrolytes from an expanded
conformation to a nearly neutral collapsed conformation and
then to an overcharged expanded conformation with increasing
concentration of multivalent ions.16 The simulation studies
have shown that the polyelectrolyte chains re-expand after the
chain collapse with increasing concentration of multivalent
ions, where the collapsed chain conformation in a middle-
salt concentration region induced by the like-charge attraction
has a direct connection to the aggregation and precipitation of
polyelectrolytes observed in experiments.17,124,125 Nevertheless,
the simulation studies have also suggested that the re-expansion
or re-dissolution of polyelectrolytes at high concentrations of
multivalent ions is not necessarily associated with a charge
inversion.124,125
Experimentally, a previous study has shown that the sodium
polystyrene sulfonate (NaPSS) solution separates into two
phases with increasing concentration of lanthanum chloride
(LaCl3), accompanied by the collapse and precipitation of
NaPSS chains.115 A re-dissolution of NaPSS and a restoration
of a single phase of the NaPSS solution are observed with
a further increase in LaCl3 concentration.115 In addition to
the reentrant behavior of polyelectrolytes observed macro-
scopically,115,116 the re-expansion of polyelectrolyte chains can
also be directly observed at a molecular level in the presence of
multivalent ions.18,126,127 By the use of fluorescence correlation
spectroscopy, Jia and Zhao have investigated the multivalent
ion-induced reentrant behavior of NaPSS at a molecular level
in aqueous solutions (Fig. 5).18 The hydrodynamic radius of
NaPSS decreases with increasing concentration of LaCl3 in
the low salt concentration regime and the NaPSS chains pre-
cipitate out the solution above a certain LaCl3 concentration.18
In the high salt concentration regime, a re-dissolution of the
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Soft Matter
Fig. 5 Hydrodynamic radius (RH) of the NaPSS single chain as a function
of the salt concentration (Cs) in the presence of different types of cations.
Reproduced with permission from ref. 18. Copyright 2009 American
Institute of Physics.
polyelectrolyte precipitates associated with a re-expansion of
NaPSS chains can be observed with increasing concentration of
LaCl3.18 The contraction and re-expansion of NaPSS chains can
be induced by the CaCl2 as well, but no precipitation of NaPSS
is observed.18 Interestingly, the re-expansion of NaPSS chains
can also be observed in the presence of monovalent CsCl, but is
difficult to understand.18 The shrinking and re-expansion of
polyelectrolyte chains in the presence of multivalent ions at a
molecular level has also been directly verified at the solid–
liquid interface using in situ atomic force microscopy.126,127
It is easily understood that the charge inversion induced by
the multivalent ions could lead to electrostatic repulsions
between polyelectrolyte chains, but the charge inversion cannot
fully explain the re-expansion or re-dissolution of polyelectro-
lytes because the Debye screening length is quite small at the
high salt concentrations.18,126,127 That is, the reentrant beha-
vior of polyelectrolytes in the presence of multivalent ions may
be related to the charge inversion, but may not be originated
from the charge inversion. In fact, the reentrant behavior of
polyelectrolytes in the presence of multivalent ions has pre-
viously been observed in the absence of charge inversion.128
Undoubtedly, more theoretical and experimental studies need
to be conducted to understand the exact mechanism behind
such an interesting reentrant behavior of polyelectrolytes.
3.2 Multivalent ion effects on polymer brushes
In general, polyelectrolyte brushes would adopt an extended
conformation in the low concentration regime of monovalent
salts due to the high osmotic pressure generated by the
counterions in the brushes.76 However, for the multivalent
salts, the grafted polyelectrolyte chains can be cross-linked by
the multivalent counterions. Therefore, polyelectrolyte brushes
would dramatically collapse upon the addition of multivalent
counterions, triggered by a significant reduction in osmotic
pressure in the brushes.129 In a previous theoretical work, the
bridging effect of multivalent ions on polyelectrolyte chains has
been included in a phenomenological mean-field model to
predict the collapse behavior of polyelectrolyte brushes in the
presence of multivalent counterions.130 A further theoretical
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Soft Matter
study has predicted that the lateral inhomogeneous structures
can be formed during the collapse of polyelectrolyte brushes
induced by the multivalent ions.131 By comparing the collapse
of polyelectrolyte brushes in a poor solvent in the absence of
multivalent counterions, a recent work by combining theore-
tical and experimental investigations has suggested that
the multivalent ion-induced electrostatic bridging of poly-
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electrolyte chains is a key driver for the formation of lateral
heterogeneous structures in the collapsed state of poly-
electrolyte brushes.132
The cross-linking effect generated by the multivalent ions
and the resultant lateral inhomogeneous structures can be
applied to tune many important properties of polyelectrolyte
brushes.10,15,41,131,133–135 Tirrell et al. have recently demon-
strated that the lubrication of SPBs can be tuned by the multi-
valent ions (Fig. 6).135 In the monovalent salt solutions, the
excellent lubrication of SPBs are related to the osmotic pressure
generated by the counterions, as shown in the left part of
Fig. 6.135 However, the friction force remarkably increases in
the presence of multivalent counterions, originating from the
multivalent ion-induced electrostatic bridging between the
grafted polyelectrolyte chains from apposing surfaces of the
SPBs at low salt concentrations (the middle part of Fig. 6).135
The right part of Fig. 6 shows that the changes in surface
topology of the SPBs are the dominating factor for the high
friction between the brush layers at the relatively high concen-
trations of multivalent ions.135
Similar to the re-expansion or re-dissolution of polyelectro-
lytes in solutions, previous theoretical studies have predicted
that the polyelectrolyte brushes re-swell in the presence
of multivalent ions.136,137 Experimentally, the re-swelling of
NaPSS brushes in the presence of multivalent counterions
was observed in both aqueous solutions and water–methanol
mixtures.20,41 At a higher content of methanol, the multivalent
counterions are more effective at inducing the re-swelling of
NaPSS brushes.41 Again, the precise cause behind the multi-
valent ion-induced re-swelling of polyelectrolyte brushes still
remains poorly understood. In addition, it is suggested that the
Fig. 6 Schematic illustration of the apposing negatively charged SPBs
(polystyrene sulfonate brushes) sliding against each other in different salt
solutions. Left part: 6 mM NaNO3, middle part: 0.01 mM Y(NO3)3, and right
part: 0.1 mM Y(NO3)3. Reproduced with permission from ref. 135.
Copyright 2018 American Association for the Advancement of Science.
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ion-specific interactions between multivalent counterions and
the charged groups of grafted polyelectrolyte chains should also
be considered when studying the structural change of polyelec-
trolyte brushes in the presence of multivalent ions.138
3.3 Multivalent ion effects on polymer gels
Mechanical properties of gels are one of the most important
factors in the applications of gels in various fields. Multivalent
ions can form coordination bonds with the ligands associated
with polymer chains, and these ion–ligand bonds can reversibly
and rapidly dissociate and associate, making multivalent ions
excellent candidates as the physical cross-linkers to prepare
hydrogels with superior mechanical properties.21,27,139–145
In Fig. 7, the hybrid hydrogels can be stretched more than
20 times with a fracture energy of B9000 J m2, which is
ascribed to a synergy of crack bridging by the covalently cross-
linked polyacrylamide network and the energy dissipation by
unzipping the ionically cross-linked alginate network by Ca2+.21
Furthermore, the deformation of the hybrid hydrogels can be
largely recovered upon unloading because of the shape memory
effect generated by the covalently cross-linked network and
the healing of internal damage by re-zipping the ionically cross-
linked network.21 By utilizing a similar strategy, the coordina-
tion bonds between Fe3+ ions and acrylic acid groups can be
ruptured to dissipate energies after the application of external
loading and can be reformed upon unloading.141 Therefore,
the prepared dual-crosslinked poly(acrylamide-co-acrylic acid)
hydrogel has excellent mechanical properties and a good self-
recovery property.141 In comparison with the divalent cations
which can only interact with the alginate chains in a two-
dimensional plane, the trivalent cations can interact with the
alginate chains to form a tighter three-dimensional network,
as a consequence, the alginate/polyacrylamide hydrogels cross-
linked by the trivalent cations are stiffer than those cross-linked
by the divalent cations.139 With this strategy, the Fe3+ ions stiffened
Ca2+–alginate/polyacrylamide hydrogels can be softened by
reducing Fe3+ to Fe2+ to fabricate the hydrogels with complex
3D structures.146
Various strategies have been proposed to prepare the aniso-
tropic hydrogels due to the great importance of anisotropy in
the applications of hydrogels.143,147–153 Previous studies have
demonstrated that the multivalent ions can be applied to
prepare the anisotropic hydrogels with the ionic cross-linking
effect.143,147,152 For the hybrid Ca2+–alginate/polyacrylamide
hydrogels, the anisotropic structures in the hydrogels can be
prepared by linearly remodeling the polymer network through a
stretch of the hydrogels, followed by a secondary cross-linking
by other types of multivalent cations, e.g., Ba2+, Al3+, and
Fe3+.152 The prepared hybrid hydrogels with anisotropic
structures have potential applications in the biomedical
fields.152 A similar strategy by using the Fe3+ ions to crosslink
the prestretched poly(acrylic acid)-co-polyacrylamide hydrogels
has been employed to prepare the anisotropic hydrogels with
improved mechanical performance.143 Besides, the anisotropic
hydrogel can also be fabricated by physically cross-linking of
semi-rigid polyelectrolyte chains with multivalent ions to form
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Fig. 7 (a) The different alginate chains are physically cross-linked by the divalent Ca2+ ions in an alginate gel. (b) The different polyacrylamide chains are
covalently cross-linked by the N,N-methylenebisacrylamide in a polyacrylamide gel. (c) The physically and covalently cross-linked networks are
intertwined and covalently connected by chemical crosslinks in an alginate–polyacrylamide hybrid gel. Reproduced with permission from ref. 21.
Copyright 2012 Nature Publishing Group.
the first uniaxially oriented network, followed by a subsequent
polymerization of neutral monomers to form the second
network.147 This method endows the prepared anisotropic
hydrogel superior mechanical properties including the excel-
lent extensibility and good shape recovery property.147
It is easy to imagine that the mechanical properties
improved by the second ionic cross-linking network would be
lost once the crosslinks formed by the multivalent ions are
removed or weakened. This makes the multivalent ions promis-
ing candidates to prepare the shape memory (SM) hydrogels.
In general, the temporary shapes of SM hydrogels are kept by
the reversible crosslinks associated with polymer chains and
the permanent shapes can be recovered after removing the
crosslinks.154 Yang et al. have synthesized a poly(acrylamide-co-
isopropenyl phosphonic acid) SM hydrogel and have demon-
strated that the temporary shape of the hydrogel is stabilized
by the interactions between the Fe3+ ions and phosphate
groups.155 The original shape of the hydrogel can be recovered
by either the chemical reduction of Fe3+ into Fe2+ by the
erythorbic acid or the extraction of Fe3+ ions from the hydrogel
by the EDTA2Na solution.155 Analogous to the redox pair of
Fe3+/Fe2+, the electrochemical reduction of Cu2+ into Cu+ can
also be applied to render the electroplastic elastomer hydrogel a
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Soft Matter
shape memory capability.156 Through the association–dissociation
of Ca2+/alginate complexes, a supramolecular polymer hydrogel
also exhibits a shape memory effect at both macroscopic and
microscopic levels.157
Besides the applications discussed above, the hydrogels
prepared with the multivalent ions can also be applied in other
fields. The excellent mechanical properties make the Ca2+ ions
cross-linked alginate/poly(acrylamide) double-network hydro-
gel a promising candidate for manufacturing the artificial
cartilage.158 The tough Ca2+–alginate/poly(ethylene glycol)
hybrid hydrogel has applications not only for the printing of
complicated 3D structures, but also for the cell encapsulation.27
Likewise, the tough Al3+–alginate/PNIPAM hybrid hydrogel has
been demonstrated as a prototype of all-hydrogel soft robotics,
where the PNIPAM chains are covalently cross-linked to form
the first network and the alginate chains are physically cross-
linked by the Al3+ ions to form the second network.159 In
principle, the multivalent ions not only act as physical cross-
linkers, but also bring their own unique properties to the
hydrogels during the preparation of hydrogels. For example,
the alginate/polyacrylamide hydrogels have obvious photolumi-
nescent properties when the lanthanide ions are employed to
prepare the hydrogels.160
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Soft Matter
4. Ionic hydrophilicity/hydrophobicity
effects
4.1 Ionic hydrophilicity/hydrophobicity effects in polymer
solutions
It has been recognized that the hydrophilic/hydrophobic
properties of polyelectrolytes are affected by both the charged
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groups of polyelectrolytes and the counterions.24 Herein, the
controlling of hydrophilic/hydrophobic properties of polyelec-
trolytes by the hydrophilicity/hydrophobicity of counterions is
defined as the ionic hydrophilicity/hydrophobicity effects.
Therefore, the hydrophilic/hydrophobic properties of strong
polyelectrolytes should be significantly changed after the
exchange of hydrophilic counterions with the hydrophobic
ones possessing a certain length of either highly fluorinated
or simple alkyl chains, e.g., perfluorooctanoate (PFO) and
alkyltributylphosphonium ([P444m]+) ions.161–167 Although
strong polyelectrolytes are usually considered as a type of
temperature insensitive polymer due to their high hydrophilicity,
it is expected that they can be made to be thermosensitive by
substituting the hydrophilic counterions with hydrophobic
ones.161–165,167 The availability of diverse hydrophobic counterions
provides a convenience to manipulate the thermosensitive proper-
ties of strong polyelectrolytes, which is of great significance for the
applications of thermoresponsive strong polyelectrolytes.161–165,167
Poly(ionic liquids) (PILs) possessing the counterions with a suita-
ble hydrophobicity have widely been employed to exemplify the
thermosensitive polyelectrolytes.24,161–165,167 The phase transition
Fig. 8 Schematic illustration of the preparation of amphiphilic random ionic copolymers through a partial counterion exchange between Cl and PF6
and the following self-assembly behaviors of the amphiphilic random ionic copolymers in aqueous solutions. Reproduced with permission from ref. 169.
Copyright 2013 The Royal Society of Chemistry.
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temperature of PILs can be adjusted by the hydrophobicity of
counterions. For example, the poly(tetrabutylphosphonium
styrenesulfonate) (poly([P4444][SS])) has a LCST of 57 1C,
whereas the poly(tributylhexylphosphonium styrenesulfonate)
(poly([P4446][SS])) is insoluble in water in the same temperature
range.162 A similar counterion hydrophobicity dependence of
thermosensitivity can be observed for the positively charged
tributyl-4-vinylbenzylphosphonium-based PILs (poly(TVBP-CnS)),
where n represents the carbon number of negatively charged alkyl
sulfonate counterions.165 Both poly(TVBP-C3S) and poly(TVBP-
C4S) are soluble in water without the LCST, whereas the poly-
(TVBP-C6S) is only slightly soluble in water.165 Nonetheless, a
suitable hydrophobicity of the counterions renders the poly(TVBP-
C5S) an obvious LCST behavior.165 In addition to the hydro-
phobicity of counterions, the thermosensitivity of PILs can also
be tuned by the composition of polymer blends, polymer concen-
tration, and external salts.163,165,167,168
Besides the thermosensitivity to polyelectrolytes, the incor-
poration of hydrophobic counterions also brings the amphi-
philicity to the polyelectrolytes. The resultant amphiphilic
polyelectrolytes can be used to prepare polymeric nano-objects
via self-assembling.169,170 Yan et al. have prepared the amphiphilic
random ionic copolymers through a partial counterion exchange of
poly(1-(4-vinylbenzyl)-3-methyl imidazolium chloride) between Cl
and PF6 (Fig. 8).169 Then, the amphiphilic random ionic copoly-
mers have been employed to prepare polymeric nanoparticles or
colloidosomes through a self-assembling strategy.169 During the
self-assembling, the polymer segments with the PF6 counterions
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tend to aggregate into the core to minimize the free energy of the
nanoparticle–water interface, while the polymer segments with
the Cl counterions form hydrophilic coronas to stabilize the
polymeric nanoparticles.169 Therefore, the partial exchange
of counterions between hydrophilic and hydrophobic ions
provides a facile method to convert homopolyelectrolytes into
amphiphilic random ionic copolymers, such that the polymeric
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in the crowded environment of SPBs.25 To realize the thermo-
responsive swelling or collapse of the SPBs, the mixtures
of small hydrophilic and large hydrophobic counterions
are employed to provide both some free space and a
certain hydrophobicity to the brushes. As a result, the wet
thickness of the SPBs can be made to be thermosensitive by
employing the mixed counterions without sacrificing the

nanoparticles can be easily prepared by self-assembling of the
random copolymers.169,170 These prepared polymeric nano-
particles have potential applications in the areas of water
purification and drug delivery.169,170
4.2 Ionic hydrophilicity/hydrophobicity effects on polymer
brushes
Similar to the strong polyelectrolytes free in aqueous solutions,
the SPBs should also be made to be thermosensitive by the
ionic hydrophilicity/hydrophobicity effects. However, SPBs have
a much higher extent of chain crowding in comparison with
that of the dilute polyelectrolyte solutions. Therefore, a high
steric barrier would be generated by the large hydrophobic
counterions in the crowded environment of SPBs after the
substitution of small hydrophilic counterions with large hydro-
phobic counterions. This would limit the conformational
change of SPBs in response to temperature. In Fig. 9, the
hydration, stiffness, and wettability of SPBs can be made to be
thermosensitive when all the small hydrophilic counterions
are replaced by the large hydrophobic counterions through a
counterion exchange.25 In contrast, the wet thickness of SPBs
is almost insensitive to temperature owing to the high steric
barrier generated by the large hydrophobic counterions
thermosensitivity of hydration, stiffness, and wettability of
the SPBs.25
On the other hand, the hydrophilicity/hydrophobicity of
counterions can be directly utilized to tune the surface wett-
ability of polyelectrolyte brushes.87,171,172 Due to the fact that
the change in surface water wettability can be strongly ampli-
fied by an increase in surface roughness,166 a switching
between superhydrophilicity and superhydrophobicity can
be achieved on the polyelectrolyte brushes modified rough
surfaces via counterion exchange.172,173 Cho et al. have modi-
fied a rough surface with the PMETAC brushes and have
achieved a reversible switching between superhydrophilicity
(o51) and superhydrophobicity (B1711) through a counterion
exchange between SCN and TFSI.173 The same counterion
exchange can only lead to a reversible change in water wett-
ability between B651 and B901 on a flat surface grafted with
the PMETAC brushes.173 Similarly, the superwettability on the
PMETAC brushes modified cotton fabric can also be reversibly
switched by counterion exchange.172 The approach to switch
the superwettability on the polyelectrolyte brushes modified
rough surfaces by the hydrophilicity/hydrophobicity of counter-
ions could find many applications in the fields of biosensors
and multifunctional textiles.172,173

Fig. 9 Schematic illustration of the counterion-tunable thermosensitivity of SPBs. P444m+ represents the tetraalkylphosphonium counterion, where the
length of three alkyl chains of the P444m+ counterions is fixed at four carbon atoms and the number of carbon atoms of the fourth alkyl chain (m) can be
changed. Here, the PSSP444m brushes represent the brushes with only the large hydrophobic P444m+ counterions, whereas the PSSNa/P4448 brushes
represent the brushes with the mixed counterions of small Na+ and large P4448+. Reproduced with permission from ref. 25. Copyright 2019 American
Chemical Society.

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4.3 Ionic hydrophilicity/hydrophobicity effects on polymer
gels
The hydrogels prepared by covalently cross-linking of thermo-
sensitive polyelectrolyte chains are also expected to be thermo-
responsive, but the physical constraint of polyelectrolyte chains
in the hydrogels would lead to some differences in response to
temperature between polyelectrolyte solutions and hydrogels.
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For example, the temperature range corresponding to the
LCST of the polyelectrolyte hydrogel becomes significantly
broad compared with that of the same linear polyelectrolyte
solution.174 It is found that the phase transition temperature of
polyelectrolyte hydrogels can be adjusted by the composition
of mixed counterions with different hydrophobicities.175 More-
over, the thermosensitive polyelectrolyte hydrogels can adsorb
a large amount of water below the phase transition temperature
and the adsorbed water can be released from the hydrogels
above the phase transition temperature driven by the volume
shrinking of the hydrogels.175 Therefore, the thermosensitive
polyelectrolyte hydrogels can be designed to reversibly uptake
and release water via the LCST-type volume transition.176
Considering that, on the one hand, a high osmotic pressure
can be generated in the polyelectrolyte hydrogels due to a high
concentration of counterions, on the other hand, the water
uptake and release of the thermosensitive polyelectrolyte
hydrogels can be readily achieved by changing temperature,
the thermosensitive ionic liquids-derived polyelectrolyte hydrogels
should be developed as smart draw agents in the forward-osmosis
(FO) desalination.13,175–177 Hu et al. have demonstrated that the
Fig. 10 Schematic illustration of a forward-osmosis desalination designed to perpetually produce desalinated water through a cyclic drawing–
dewatering process by employing the thermoresponsive PIL hydrogel as the smart draw agent. Reproduced with permission from ref. 13. Copyright 2016
John Wiley and Sons.
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thermosensitive PIL hydrogels can produce a reasonable water
flux during the FO desalination below the phase transition
temperature and the desalinated water can be effectively released
from the hydrogels above the phase transition temperature.177
In Fig. 10, we have demonstrated that the thermoresponsive PIL
hydrogels can be developed as smart draw agents to perpetually
produce desalinated water through a cyclic drawing-dewatering
process based on the FO desalination.13 The collapsed PIL hydro-
gel preconditioned at a temperature above the volume transition
temperature is used to draw the fresh water from the feed solution
across the membrane at a temperature below the volume transi-
tion temperature (part I). A swollen PIL hydrogel is obtained after
this FO process (part II). As the temperature is increased above the
volume transition temperature again, the swollen PIL hydrogel
collapses accompanied by a release of desalinated water from
the hydrogel (part III). At the same time, the draw agent can be
regenerated by a separation of the PIL hydrogel from the
recovered liquid water.
5. Summary and outlook
In this review, we have discussed the ionic effects on synthetic
polymers from solutions to brushes and gels. For the neutral
polymers, the ion specificities are determined by both the
direct and indirect ion–polymer interactions. The direct ion–
polymer interactions are dominated by the nature of the bound
ions. The indirect ion–polymer interactions are affected by not
only the ions but also the solvent composition. The specific ion
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effects on charged polymers are mainly dominated by the
specific ion-pairing interactions. It has been demonstrated that
the properties of polymer solutions, brushes, and gels can be
tuned with specific ion effects. The most prominent effect
exhibited by the multivalent ions is the ionic cross-linking
effect, which can be used to control the polyelectrolyte con-
formation in solutions, the surface properties of polyelectrolyte
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brushes, and the mechanical properties of polyelectrolyte gels.
The nature of the reentrant behavior of polyelectrolytes in the
presence of multivalent ions still remains elusive. The ionic
hydrophilicity/hydrophobicity effects not only can be used to
make polyelectrolytes thermosensitive, but also can be applied
to prepare polymeric nano-objects in solutions and to control
the wettability of polyelectrolyte brush-modified surfaces.
The current challenges and future directions of these three
subclasses of extensively investigated ionic effects and the not
well-studied ionic hydrogen bond effects are discussed below:
(1) Undoubtedly, the specific ion effects on synthetic poly-
mers still remain incompletely understood.9 The development
of appropriate theories to fully understand both the direct and
indirect specific ion–polymer interactions is desirable in future
studies. On the other hand, it has been recognized that the
complex solution environments such as salt mixtures, solvent
mixtures, and macromolecular crowding have important influ-
ences on the ion specificities of polymers.22,40,42,49,50,52–54,178–181
In reality, these complex solution environments are extensively
existed, but the understanding of specific ion effects in these
complex environments is just at the initial stage. More studies
need to be conducted to have a better understanding of the
specific ion effects on polymers in these complex environments.
Besides the polymer solutions, brushes, and gels, the
specific ion effects are anticipated to be further applied to
control the properties of other important polymeric materials.
For instance, the natural environments such as seawater and
soils contain a large amount of different types of ions.1–3 These
ions could strongly influence the activities of the enzymes
secreted from microorganisms scattered in the natural
environments.182–184 Therefore, the specific ion effects are
expected to be used to control the enzymatic degradation of
biodegradable polymeric materials in natural environments
including the polymeric antibiofouling materials in the marine
environment185 and the polymeric mulch films in the soil
environment. As the strength of hydrophobic interactions
is dependent on the nature of the ions presented in the
systems,186 it is expected that the specific ion effects can also be
used to improve the performance of polymeric organocatalysts by
tuning the affinities between catalysts and substrates.187
The super-chaotropic behavior of nano-ions has recently
received increasing interest.188–191 Due to the large ion size
and low ionic volume charge density, the mechanism of spe-
cific ion effects exerted by the super-chaotropic nano-ions may
be somewhat different from that for the small chaotropic ions.
For example, the ion polarizability is considered as one of the
most important factors in the determination of specific ion
effects for the small chaotropic ions, but it only plays a weak role
in ion specificities for the super-chaotropic nano-ions.189,192–194
4100 | Soft Matter, 2020, 16, 4087--4104
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Soft Matter
Therefore, the future studies on synthetic polymers with super-
chaotropic nano-ions may provide some new insights into the ion
specificities of polymers.
(2) Multivalent ion effects. The precise cause of the reentrant
behavior of polyelectrolytes in the presence of multivalent ions
still remains unclear. Recently, several research groups have
reported that the electrostatic decay length is increased at
high salt concentrations, though the origins of the increased
electrostatic decay length are under extensive discussion.195–206
Such an increased electrostatic decay length might be respon-
sible for the reentrant behavior of polyelectrolytes in the
presence of multivalent ions.207 Furthermore, the reentrant
behavior of polyelectrolytes is dependent on the nature of
multivalent ions with the same ionic valency,20 which means
that specific ion effects may be involved in this interesting
phenomenon. Obviously, more work needs to be performed to
understand the reentrant behavior of polyelectrolytes in the
presence of multivalent ions. In addition, the effects of multi-
valent ions on the formation of inhomogeneous structures in
polyelectrolyte brushes and the improvement of mechanical
properties of polyelectrolyte gels are also desirable for further
studies.
(3) Ionic hydrophilicity/hydrophobicity effects. More versatile
polymeric nano-objects could be prepared via a self-assembling
strategy if the amphiphilic block ionic copolymers can be
obtained through the counterion exchange. Besides, the control-
ling of superwettability of the polyelectrolyte brush-modified
rough surfaces with ionic hydrophilicity/hydrophobicity effects
can be further applied to prepare smart devices, e.g., smart glass
displays.166 On the other hand, there is still a big challenge
to produce desalinated water from seawater with the thermo-
sensitive PIL hydrogels as the smart draw agents in the FO
desalination. The seawater which is usually simulated as 0.6 M
NaCl solution has a much higher osmotic pressure compared
with that of the brackish water (e.g., 2000 ppm NaCl
solution).208,209 The key to achieving the production of desali-
nated water from seawater is to increase the osmotic pressure of
polyelectrolyte hydrogel-based draw agents without sacrificing
their thermosensitivity. Two methods of either using the small
highly fluorinated counterions to replace the large alkyl counter-
ions or the combination of the small counterions with a certain
hydrophobicity and the strong ion-pairing interactions79 may be
the feasible choices.
(4) Ionic hydrogen bond effects. When the counterions
possess hydrogen bond donors or acceptors, they not only
can electrostatically interact with the oppositely charged groups
of polyelectrolytes, but also can interact with polyelectrolytes
via hydrogen bonding. The corresponding hydrogen bond
effects exerted by the counterions are defined as the ionic
hydrogen bond effects.10 It has been demonstrated that the
properties of SPBs can be tuned by pH through the ionic
hydrogen bond effects generated by the hydroxide and hydro-
nium ions.10,14,77 In fact, besides these two types of ions, many
other types of ions also have hydrogen bond donors or acceptors.
Therefore, a great deal remains to be learned about the tuning
of polyelectrolyte properties with ionic hydrogen bond effects
This journal is © The Royal Society of Chemistry 2020

Soft Matter
beyond the hydroxide and hydronium ions. Additionally, the ionic
hydrogen bond effects and other subclasses of ionic effects may
coexist in one polyelectrolyte system. Thus, the interplay between
the different ionic effects may have a strong influence on the
properties of polyelectrolytes.
Conflicts of interest
Published on 14 April 2020. Downloaded by University of Wisconsin - Madison on 9/13/2020 10:41:57 AM.
There are no conflicts of interest to declare.
Acknowledgements
The financial support of the National Natural Science Founda-
tion of China (21873091, 21622405, 21574121), the Youth
Innovation Promotion Association of CAS (2013290), and the
National Synchrotron Radiation Laboratory (UN2018LHJJ) is
acknowledged.
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