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CO2-responsive polymeric materials: synthesis,

self-assembly, and functional applications
Cite this: Chem. Soc. Rev., 2016,
45, 4391
Ali Darabi,†a Philip G. Jessop*b and Michael F. Cunningham*ab

Received 25th November 2015
DOI: 10.1039/c5cs00873e
www.rsc.org/chemsocrev
CO2 is an ideal trigger for switchable or stimuli-responsive materials because it is benign, inexpensive, green,
abundant, and does not accumulate in the system. Many different CO2-responsive materials including polymers,
latexes, solvents, solutes, gels, surfactants, and catalysts have been prepared. This review focuses on the
preparation, self-assembly, and functional applications of CO2-responsive polymers. Detailed discussion is
provided on the synthesis of CO2-responsive polymers, in particular using reversible deactivation radical
polymerization (RDRP), formerly known as controlled/living radical polymerization (CLRP), a powerful
technique for the preparation of well-defined (co)polymers with precise control over molecular weight
distribution, chain-end functional groups, and polymer architectural design. Self-assembly in aqueous
dispersed media is highlighted as well as emerging potential applications.

1. Introduction the first report of a CO2-switchable polymer was published in

In many applications, a material such as a polymer is required to
react to a specific stimulus or trigger. Stimuli-responsive polymers
exhibit reversible changes in their physical or chemical properties
in response to external triggers such as temperature, pH, light, or
voltage.1 However, there are major limitations in applying these
triggers including economic and environmental costs and product
contamination.2 However CO2, which is a benign, inexpensive,
abundant, and non-toxic trigger for stimuli-responsive materials,
has received increasing attention in recent years.3 Because of its
green nature, CO2 has already been applied as a green solvent
in polymer synthesis in both homogeneous and heterogeneous
polymerizations.4 Also, supercritical carbon dioxide (scCO2),
which is an environmentally friendly, non-flammable, and
inexpensive solvent has found many new areas of interest in
polymer synthesis due to the fact that as a polymerization
medium it has negligible chain transfer and does not accumulate
in the reaction.5,6
Due to the very interesting properties of CO2 as a trigger,
CO2-responsive polymers have found potential applications in
different areas including latexes,7–13 gels,14–17 CO2 capturing and
monitoring,18–23 separation,24 encapsulation,25 forward osmosis,26,27
CO2-switchable vesicles,28–31 and CO2-switchable worm-like
micelles.32–36 CO2-responsive materials and CO2-responsive
polymers have been reviewed.3 To the best of our knowledge,
1986. Moore and Lefevre at The Dow Chemical Company wrote
a patent describing a method for shear coagulation of latex
resins stabilized by fatty acid based stabilizers.37 In this
method, solids were recovered from a pH-responsive latex by
passing CO2 through the dispersion to destabilize the latex by
neutralizing the ionized fatty acid groups, and then applying
high shear to separate the solids. Most subsequent research on
CO2-switchable materials has focussed on basic groups such as
amines and amidines.
The covalent bonding of CO2 with primary amines is a
thermally reversible reaction that produces carbamate salts.
Rudkevich and coworkers used this reaction for the preparation of
a range of CO2-switchable polymers including switchable fluores-
cent supramolecular polymers.38,39 Weiss and coworkers used the
same reaction in polyamine-based gels; a facile isothermal method
was developed for the cleaning of several art objects.40
In 2006, we introduced CO2-switchable surfactants based on
long-chain alkylamidines, which could be easily switched on
and off in aqueous media in the presence of CO2 (Fig. 1).7,41 In this
case, bicarbonate salts rather than carbamate salts were formed
upon CO2 addition. Alkylamidines are protonated (switched on)
by bubbling CO2 in their aqueous solutions and converted to
bicarbonate salts. In the protonated form they can stabilize latex
particles due to the existence of electrostatic repulsive forces.

a
Department of Chemical Engineering, Queen’s University, Kingston, Canada.
E-mail: Michael.Cunningham@queensu.ca
b
Department of Chemistry, Queen’s University, Kingston, Canada.
E-mail: philip.jessop@chem.queensu.ca Fig. 1 CO2-switchability of amidine-based switchable surfactants (R = C8
† Current address: Arkema Research and Development Center, Functional to C16 alkyl chain).7 Reproduced from ref. 7 with permission from AAAS
Additives, King of Prussia, PA USA. publications.

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Fig. 2 Number of annual publications on CO2-switchable polymers in the
past decade.
When they are deprotonated (switched off) by removal of CO2
from the system, the latex is destabilized and coagulates.
Because of the several advantages of CO2 over other triggers, the
number of publications on CO2-switchable (or CO2-responsive)
materials has increased rapidly during the last few years (Fig. 2).
There are only a few reviews related to CO2-switchable solvents and
Ali Darabi worked for the Xerox
Research Centre of Canada (XRCC)
before moving to Queen’s University
in 2011 to pursue his PhD in
Chemical Engineering under the
supervision of Prof. Michael F.
Cunningham. The major focus of
his study was synthesizing CO2-
responsive polymers by nitroxide-
mediated polymerization (NMP) in
dispersed media. After graduation,
he joined the Arkema Research and
Development Center in King of
Ali Darabi
Prussia, Pennsylvania USA.
Philip Jessop is the Canada
Research Chair of Green Chemistry
at Queen’s University in Canada
and the Technical Director of
GreenCentre Canada, a centre for
the commercialization of green
chemistry technologies. His
research interests include green
solvents and the chemistry of CO2
and H2. Recent distinctions include
the Canadian Green Chemistry &
Engineering Award (2012) and the
Philip G. Jessop Eni Award for New Frontiers for
Hydrocarbons (2013).
4392 | Chem. Soc. Rev., 2016, 45, 4391--4436
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surfactants,2 CO2-responsive polymers,3 and CO2-responsive
block copolymers.42 In this comprehensive review we focus on the
synthesis of CO2-switchable polymers by different polymerization
techniques, self-assembly of synthesized CO2-switchable polymers in
aqueous media, and functional applications of these materials. The
total number of publications on CO2-switchable polymers since 2005
is about 160 and most of them are covered in this review.
2. Triggers for responsiveness
Smart or stimuli-responsive polymers are classified based on
the trigger (stimulus) that they are sensitive to. For example,
some polymers are sensitive to temperature while others are
responsive to pH. Some polymers are responsive to multiple triggers.
Other triggers include light, oxidants, redox potential, and magnetic
fields. CO2 has only recently emerged as a popular trigger.
2.1. Temperature
Temperature-responsive polymers are among the most common
stimuli-responsive polymers. These polymers change their physical
and/or chemical properties in response to variations in tempera-
ture. While all polymers are inherently temperature-responsive due
to the melting point and glass transition temperature, the phrase
‘‘temperature-responsive’’, when applied to polymers, usually
refers to temperature-dependent changes in the water/polymer
binary phase behaviour. The lower critical solution temperature
(LCST) of a polymer in water is a distinguishing property of
thermo-sensitive polymers. Poly(N-isopropylacrylamide), PNIPAM, is
the most studied temperature-sensitive polymer.43,44 The interested
reader is referred to several excellent reviews on temperature-
responsive polymers.43,45–47
2.2. pH
pH-Sensitive polymers are able to accept or donate protons in
response to pH changes.48 The changes in pH can be induced by
the addition of acids and bases. When uncharged pH-responsive
groups in the polymer structure become charged in response to
changes in pH, polymer chains are extended by electrostatic
repulsion forces created by identical charges. The transition
Michael Cunningham is a professor
of Chemical Engineering at Queen’s
University and cross-appointed to
the Department of Chemistry. He
holds an Ontario Research Chair in
Green Chemistry and Engineering.
His research interests include
CO2-switchable polymers, polymer
colloids and nanoparticles, and
the synthesis of hybrid composite
materials made of natural polymers
grafted with synthetic polymers. He
Michael F. Cunningham is Chair of the International
Polymer Colloids Group (IPCG).
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from a collapsed state to an extended state is reversible. At a
specific pH, the degree of protonation of the polymer changes
significantly in response to a small change in the pH. At this pH,
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known as the pKa, 50% of the functional groups are ionized.45
Poly(diethylamino)ethyl methacrylate, PDEAEMA, poly(dimethyl-
amino)ethyl methacrylate, PDMAEMA, and poly(4 or 2-vinyl-
pyridine), (PVP), are common pH-responsive polybasic polymers.46
Chitosan is another pH-responsive polymer. It is a biodegradable
and biocompatible bio-derived polymer, which is produced by
alkaline deacetylation or enzymatic degradation of chitin (the
second most abundant polysaccharide after cellulose).49
One of the main problems experienced with pH-responsive
polymers is their contamination with salts after multiple
protonation–deprotonation cycles with acids and bases. Some
acids and based are also hazardous materials.
2.3. CO2
Although most of the publications describing stimuli-responsive
polymers are related to temperature, pH, and light-sensitive
polymers, carbon dioxide (CO2) has attracted increasing attention
as a new and promising trigger with unique advantages. CO2 is an
environmentally-friendly trigger and is inexpensive due to its
abundance.
CO2 is also a biocompatible and low toxicity trigger. In our
respiratory system, primary and secondary amines reversibly
trap CO2 by the formation of ammonium carbamates.29,50,51
It can also be used as the starting material for producing
biodegradable polymers.52 One of the primary advantages of
CO2 in the synthesis of CO2-responsive latexes and polymers is
that this trigger is not accumulated in the system because
addition and removal of CO2 can be achieved easily and without
salt accumulation. However, the solubility of CO2 in water
decreases significantly with higher temperatures and therefore
it cannot be effectively used as a trigger at atmospheric pressure
at temperatures >B65 1C which are desirable or necessary
for some polymerization reactions. (Applying pressure to the
polymerization increases CO2 solubility in water and allows
effective triggering at higher temperatures.) Furthermore, since
carbonic acid is a weak acid, the range of pH achievable by
varying the CO2 concentration is limited while a wide range of
pH can be achieved by using strong acids or bases. However,
working with CO2 is safer and easier than using acids or bases,
and its environmental impact is negligible.
2.4. Other triggers
There are other stimuli-responsive polymers that are sensitive to
different triggers. For example, light-sensitive polymers change
their properties if they are irradiated with light of a specific
wavelength.53 However, UV light is not an effective trigger for
large scale applications because is decays rapidly at long
distances or in media with large RI (refractive index) hetero-
geneity, or absorbance.54 Polymers containing azobenzene
groups are the most studied examples of photo-responsive
polymers.55 Chemo-responsive polymers are sensitive to chemical
changes in the environment.56 Redox-responsive polymers contain
redox-responsive groups that respond to the addition of oxidants or
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reductants or applied potentials.57 Some polymers are sensitive
to glucose levels and have potential applications in the insulin
delivery for the treatment of diabetes.46 For example, Shi et al.
synthesized glucose-responsive micelles using the self-assembly
of two block copolymers including poly(N-isopropylacrylamide)-
b-poly(aspartic acid-co-aspartamidophenylboronic acid) (PNI-
PAM-b-P(Asp-co-AspPBA)) and poly(ethylene glycol)-b-poly(aspartic
acid-co-aspartamidophenylboronic acid) (PEG-b-P(Asp-co-AspPBA)).
At a specific weight ratio of PNIPAM/PEG = 1.5, the block
copolymers are converted to a glucose-responsive core–shell–
corona self-assembly, enabling controlled release of insulin
adjustable by the concentration of glucose.58
2.5. Multi-stimuli responsive systems
Some polymers can respond to more than one trigger, making
them potentially more versatile.59,60 For example, PDMAEMA is
a pH-responsive polymer because of the presence of tertiary
amine groups in the structure of the polymer. However, it also
has an LCST around 40 1C,61 which makes it temperature-
responsive as well. Copolymerizing a temperature-responsive
polymer with a pH-responsive polymer gives a polymer with dual
responsiveness.27,62 Tang et al.63 synthesized a temperature, pH,
and light-sensitive polymer by atom-transfer radical polymeriza-
tion (ATRP) of DMAEMA with an azobenzene moiety. Another
example involves the use of pentafluorophenyl end-capped
poly(ethylene glycol) aqueous solutions which exhibit a switch-
able LCST.64 In this system, the LCST increases from 24.5 to
26 1C when dissolved CO2 is replaced by oxygen. The process is
reversible and the LCST returns to the original value when the
PF–PEG–PF aqueous solution is exchanged with O2.64
3. Materials containing CO2-responsive
moieties
To synthesize a CO2-responsive polymer, a moiety with CO2-
responsiveness is required. This moiety can be a surfactant,
monomer, initiator, or solvent. In each case, CO2-switchability
is induced by the presence of a CO2-functional group such as
tertiary amine, amidine, guanidine, imidazole, or carboxylic
acid (Fig. 3).
3.1. CO2-switchable functional groups
The main CO2-switchable functional groups are those that
switch from neutral to cationic, anionic, or carbamate salts.
Fig. 3 Structure of CO2-switchable functional groups, top; from left to
right: tertiary amine, amidine, guanidine, bottom: imidazole, carboxylic
acid.
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3.1.1. CO2-switchable functional groups that switch from
neutral to cationic. Guanidines, amidines, tertiary amines, bulky
secondary amines, and bulky primary amines in the presence of
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water switch from neutral to cationic when reacting with CO2.
Guanidines. Guanidines are the most basic CO2-switchable
functional groups and therefore require more energy (higher
temperature for longer time) for converting the bicarbonate salt
to the neutral form. The inclusion of an aromatic substituent
tempers the basicity. Guanidines containing N–H bonds could
form carbamates instead of, or in addition to, bicarbonate
salts.10 However, the greater temperatures required to switch
guanidinium bicarbonate or guanidinium carbamate salts back
to neutral guanidinium would be an advantage for applications
where high temperatures are required.
Amidines. Amidines, which are stronger bases than amines
but weaker than guanidines,65 can be reversibly protonated and
deprotonated in the presence of water by addition and removal
of CO2 (e.g. Fig. 1).2,7 However, this assumes that the amidine
contains no N–H bonds; if such a bond exists then a carbamate
salt might be obtained instead of, or in addition to, the
bicarbonate salt.2 Amidines are switched to bicarbonate salts more
quickly than are tertiary amines but the reverse process is more
endothermic and therefore more difficult and slower, because of
the greater basicity.10 The basicity of amidines can be reduced by
the inclusion of an aromatic substituent on either nitrogen or the
central carbon, giving amidines that behave more like tertiary
amines in terms of their responsiveness to CO2.10 Because of their
CO2-responsiveness, they have been used in CO2-switchable
amidine-containing (co)polymers.66 Complex synthesis routes and
the risk of decomposition by hydrolysis are typical challenges
associated with amidines.3 Lowe and coworkers have reviewed
applications of amidines as CO2-switchable building blocks for
synthesizing CO2-switchable polymers in order to apply them in the
area of CO2-switchable latexes, purification, and switchable self-
assembly of polymeric nanoparticles.67 Fig. 4 shows some general
approaches for the synthesis of amidines.
Imidazoles and imidazolines are examples of cyclic amidines
with a 5-membered ring. Imidazoles having a long alkyl chain
Fig. 4 General approaches for the synthesis of amidines.68 Reproduced
from ref. 68 with permission from the RSC.
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are switchable surfactants, exhibiting surfactant-like behaviour
only when CO2 is present.11
Amines. Amines are weaker bases than alkylguanidines and
alkylamidines. A common criteria to compare basicity is the
dissociation constant (pKaH) of the conjugate acid; a larger pKaH
indicates a stronger base.69 In water, tertiary, bulky secondary,
and bulky primary amines are responsive to CO2 because they
are converted to the corresponding bicarbonate salt.10 However,
they cannot be used at high temperatures because the percent
protonation is low at high temperatures unless the CO2 pressure
is increased.2 For example, in our labs, we attempted to perform
nitroxide-mediated polymerizations (NMP) of DEAEMA in water
under a CO2 atmosphere.70 DEAEMA was initially protonated by
bubbling CO2 in the aqueous solution of DEAEMA at room
temperature, but after the start of the reaction at 90 1C, it was
rapidly deprotonated. Facile deprotonation of bicarbonate salts
of tertiary amines is a major advantage for their usage in
applications where rapid switching back to the neutral form is
required.2 Another advantage of tertiary amine compounds is
their commercial availability and lower cost. Bulky secondary
and bulky primary amines are also CO2-switchable by conversion
into bicarbonate salts, because the bulky group inhibits carbamate
formation. Typically one secondary alkyl group, like an isopropyl
group, attached to the nitrogen atom is sufficient to prevent
carbamate formation. These amines switch more rapidly than do
tertiary amines, but if a secondary amine has two bulky groups
attached to the nitrogen atom, such as in diisopropylamine, then
the rate advantage is lost. Secondary and primary amines also have
the advantage of faster biodegradation than tertiary amines.
3.1.2. CO2-switchable functional groups that switch from
neutral to anionic
Carboxylic acids and phenols. In water, these functional
groups are neutral in the presence of CO2 and anionic in its
absence. Depending on the desired concentration and other
factors, they can be introduced in the acid (uncharged) form or
in the anionic form, typically as a sodium salt. At pH values
below the midpoint, which usually corresponds to the pKa, the
group is largely in the neutral form. However, the midpoint can
be significantly higher than the pKa if the neutral form has
limited solubility in the aqueous solution.71
3.1.3. CO2-switchable functional groups that switch from
neutral to carbamate salts. Some CO2-functional groups, such
as amines having N–H bonds and no bulky group adjacent to
the nitrogen, switch from neutral to carbamate salts. This
category of CO2-switchable functional groups may also include
amidines and guanidines that contain an N–H bond.
3.2. CO2-switchable surfactants
Surfactants are essential components of emulsion, miniemulsion,
and microemulsion polymerizations.72 The main role of surfactants
in all these polymerization systems is stabilizing latex particles.73
However, after polymerization, the existence of surfactant in the
final product is problematic. Removal of the surfactant by washing
processes is not always perfect and most often some of the
surfactant remains in the purified polymer. In general, the
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better the surfactant is at stabilizing latex particles, the more
difficult is its removal from the system.10 Residual surfactants
can alter the properties of the final product;7 for example, in
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Table 1 Solubility of CO2 in water at different temperatures and 100 kPa
partial pressure.97 Reproduced from ref. 75 with permission from AIP
publishing LLC

film forming applications, migration of the residual surfactant 1000  mole fraction of CO2
has a negative effect on the properties of the final product.74–76 Temperature (1C) in liquid phase
Latex destabilization (for obtaining latex powder) is conventionally 0 1.337
performed by addition of acid, base, and salt depending on the type 5 1.123
10 0.950
of surfactant employed in emulsion polymerization.1 Therefore, 15 0.814
post-washing steps are required for removing these chemicals and 20 0.704
a large volume of waste water is produced, which leads to the 25 0.614
30 0.541
increase in the cost and environmental impact of the process.12 35 0.481
Another issue in latex production is transportation of the 40 0.431
latex from the point of production to the point of consumption. 45 0.389
50 0.354
Because a large fraction of the mass of a latex is water, shipping 55 0.325
latex from one location to another means additional cost for 60 0.300
the transportation of water.77 65 0.279
70 0.261
Switchable surfactants can address the above-mentioned 75 0.245
concerns. These surfactants can be switched on (active state) 80 0.232
or switched off (inactive state) as needed.2 This is an advantage 85 0.221
90 0.211
in latex production since the stability of the latex is not always 95 0.203
necessary. So far, many different types of switchable surfactants 100 0.196
have been prepared which mainly differ in the type of trigger
that is used in the switching on and off process. Brown et al.78
have recently reviewed stimuli-responsive surfactants. They include
light-sensitive surfactants,79–83 acid/base-sensitive surfactants84–88
and redox-sensitive surfactants.89–94 In most cases, addition of
acid, base, oxidant, or reductant is required, which causes
environmental impact due to the wastewater produced in
subsequent washing steps. In the case of light sensitive surfac-
tants, the reaction media should be transparent,10 which is
unlikely in many polymers or latex suspensions. Switchable
peptide surfactants (pepfactants), which are based on a series
of amino acids, are often expensive.95,96
To overcome these problems, CO2-switchable surfactants, as
a new class of stimuli-responsive surfactants, were introduced.7
In aqueous media, pH can be changed by addition of CO2, with
the degree of change in pH depending on the concentration of
dissolved CO2 in the aqueous phase. However, the solubility of Fig. 5 The conductivity of a DMSO solution of a switchable surfactant
with R = C16H33 in Fig. 1 as a function of time during three cycles of
gases in liquids depends on temperature, pressure, and pH. As
treatment with CO2 followed by argon.7 Reprinted from ref. 7 with
temperature increases, the solubility of CO2 in water decreases, permission from AAAS publications.
while as the pressure increases the solubility of CO2 increases.97
A model has been developed based on Henry’s law for the
investigation of the solubility of CO2 in water at different solution over several cycles of purging CO2 and N2 (Fig. 5).
temperatures and pressures.98 However, the data in Table 1 Conductivity increases with protonation and decreases with
assume that no additional reagents are present; if some CO2- deprotonation due to the increase and decrease in the number
switchable species are present at significant concentrations, of charged molecules, respectively.7
this may significantly change the solubility of the CO2. Because deprotonation is an endothermic process, heat is
Long-chain alkyl amidines can be protonated by bubbling generally required to facilitate the deprotonation reaction
CO2 into their aqueous solution.7 In this state, they can behave (Fig. 6 and Table 2). Thus the greater the protonation enthalpy,
like surfactants because they have a charged hydrophilic head the more heat must be supplied to switch the compound back
and a long hydrophobic tail (Fig. 1). Therefore, they can be to its neutral form.
employed as stabilizers in emulsion polymerization.7 The removal The performance of long alkyl-chain molecules as CO2-switchable
of CO2 to ‘‘switch off’’ the surfactant can be simply performed surfactants depends largely on the nature of their head group.
by purging with a nonacidic gas such as nitrogen, argon, or air. The structure of the head group can change solubility, basicity,
To confirm protonation–deprotonation of the CO2-switchable heat of protonation, and the heats of CO2-switchability of the
surfactants, an easy way is measuring conductivity of their surfactant.65

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Fig. 6 Reaction of amidines and amines with CO2 and water to form
bicarbonate salts.10 Reproduced from ref. 10 with permission from ACS
publications.
Table 2 Heat of protonation of CO2-switchable surfactants and esti-
mated pKaH values for selected bases.65 Reproduced from ref. 65 with
permission from the RSC
Molecule Heat of protonation (kJ mol1) pKaH (H2O scale)
71  1 12.2
47  0.8 11.1
54  0.7 11.0
48  0.3 10.8
83  0.2 13.8
C8H17NMe2 53  0.5 10.0
Note: pKaH values are estimates. See ref. 65 for details.
CO2-switchable surfactants have been used in emulsion
polymerization for the stabilization of the original emulsion
and the product latex particles.7,10,99 However, in some cases,
the surfactant is not available commercially and needs to
be synthesized. For example, N,N-didodecylacetamidinium
bicarbonate, a double-tailed cationic surfactant, was synthe-
sized by reacting dimethylacetamide dimethylacetal with
dodecylamine and then with dry ice.100 (N-Amidino)dodecyl
acrylamide (DAm) was employed as a CO2-switchable reactive
surfactant for the preparation of coagulatable/redispersible
polystyrene latexes.1 Redispersion of the latex was achieved by
purging with CO2, while coagulation was performed by purging
with N2 and heating to remove CO2 and neutralize the latex
particles. However, the amidine group was partially hydrolyzed
under basic conditions.
Zhu’s group prepared poly(DMAEMA-b-MMA) via a two-step
solution RAFT polymerization and used it in the protonated
form (initial protonation was performed by addition of HCl)
as a CO2-switchable surfactant in an emulsion polymerization
of MMA.77,101 The latex stability depended on the diblock
copolymer composition, and the latex particle size decreased
with increasing weight fraction of MMA (FMMA). After the latex
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Fig. 7 Coagulation and redispersion of polystyrene latex in the presence
of a CO2-switchable surfactant and initiator.9 Reproduced from ref. 9 with
permission form ACS publications.
had been neutralized with caustic soda, the coagulated latex
was redispersible if FMMA o 46%.
We have prepared CO2-switchable PS and PMMA latexes by
using CO2-switchable surfactants.8,9,102 Coagulation and redis-
persion of the latex particles was achieved by removal and
addition of CO2 (Fig. 7). The results showed that when both
initiator and surfactant are CO2-switchable, redispersion is most
effective and almost full recovery of the zeta potential and size
distribution of latex particles is obtained.9 Similarly, PMMA latexes
were prepared using long chain alkyl amidine CO2-switchable
surfactants, and the effects of several parameters including the
type and amount of surfactant and initiator, and solid contents on
the particle size and zeta potential were investigated.8 The resulting
latex particles were 50 to 350 nm in size and could be easily filtered
to obtain dry polymer powder.
Other structures of CO2-responsive surfactants have been
reported. For example, CO2-switchable surfactants bearing imidazole
groups can be converted to imidazolinium bicarbonate cationic
surfactants after protonation by CO2.103,104 Also, N,N-dimethyl-N0 -
(pyren-1-ylmethyl) acetimidamidinium (PyAH+) was used as a
CO2-responsive dispersant bearing a pyrene moiety and an
amidinium cation.105 It was then attached through p–p inter-
actions onto single-walled carbon nanotubes (SWNTs), resulting
in improved dispersion in water (Fig. 8). The solubility of the
SWNTs was reversible by addition and removal of CO2.
Commercially available long-chain tertiary amines (dimethyl-
hexadecylamine, DHA, and dimethyldodecylamine, DDA) were
used as CO2-switchable surfactants for the preparation of PS and
PMMA nanocapsules with aqueous cores from an emulsion.106
The core of the particles can be switched from a hydrophobic
state to a hydrophilic state by applying CO2 (Fig. 9).
Fig. 8 Interconversions between PyAH+ and PyA.105 Reprinted from
ref. 105 with permission from ACS publications.
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Fig. 9 Scheme illustrating the applications of long-chain tertiary amines:
reversible aggregation/re-dispersion of polymer latexes could be achieved
by alternately using CO2 or argon (left); aqueous-core polymer capsules
could be obtained in aqueous dispersions by charging CO2 when tertiary
amines were used as a liquid core. The bottom shows the chemical
structures of uncharged and charged DDA.106 Reprinted from ref. 106
with permission from the RSC.
The effect of the molecular structure of two CO2-switchable
surfactants N 0 -dodecyl-N,N-dimethylacetamidinium bicarbonate,
C12N, and N 0 -(2-(2-(dodecyloxy)ethoxy)ethyl-N,N-dimethylacet-
amidinium bicarbonate, C12E2N) on the coagulation and redis-
persion behaviour of polystyrene latexes was investigated in
detail by the Jessop and Cunningham groups.107 The structures
of these surfactants are shown in Fig. 10. The zeta potential and
surface coverage of PS latexes prepared with C12N decreased as
expected when CO2 was removed but did not return to the
initial value when CO2 was reintroduced to the system. How-
ever, in the case of latexes prepare with C12E2N, the initial zeta
potential and surface coverage was recovered. Latexes with
C12E2N surfactant respond more quickly and completely to N2
and CO2 than those with C12N surfactant (Fig. 11). According to
the investigations of adsorption isotherms, the head groups of
surface-bound C12E2N protrude into the aqueous phase, but
surface-bound C12N tends to lie flat against the hydrophobic
surface when the switchable surfactant is neutral. Thus, when
CO2 is bubbled into the aqueous phase, the head group of
C12E2N is readily protonated while C12N is not, due to its
effectively higher pKaH from being in a hydrophobic environ-
ment. Therefore, the design of the surfactants has a significant
effect on switchability.107
While CO2-responsive surfactants have proven to be effective
in stabilizing latexes, they do have disadvantages. Like any
traditional surfactant, they are not covalently bound to the
particle surface and are therefore subject to migration on the
particle surface which can cause stability problems, or eventual
leaching into the environment. Since most surfactants are toxic
Fig. 10 The switching of surfactants C12E2N and C12N between their
neutral and surfactant forms.107
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Fig. 11 The z potential of polystyrene particles as a function of time
during destabilization using N2 bubbling through the suspension at
80 1C followed by redispersion using CO2 bubbling through the mixture
at room temperature.107 Reprinted from ref. 107 with permission from ICE
publishing.
(to aquatic species for example), leaching can be a serious
concern. A preferred solution, to be discussed later in this review, is
to covalently bind the switchable groups, which improves colloidal
stability and the redispersibility of aggregated particles, and
prevents surfactant leaching.
Conventional surfactants such as SDS and CTAB are inex-
pensive and widely used in processes and formulations but are
not CO2-responsive. Replacing them with CO2-responsive sur-
factants could be problematic because of higher surfactant cost
and the need to reformulate well-established processes and
formulations. However, it has been shown that the addition of
a CO2-responsive additive such as a water-soluble amine into
the aqueous phase makes conventional surfactant-stabilized
emulsions and suspensions become CO2-responsive. Su et al.
added DMEA as a CO2-switchable additive to a dodecane/water
emulsion, which had been prepared using SDS surfactant.
Without DMEA, CO2 could not break the emulsion but when
DMEA was present in the solution, bubbling CO2 caused
destabilization of the emulsion, attributed to an increase in
the ionic strength of the solution.54 The process was reversible
and removal of CO2 resulted into the creation of a stable
emulsion (Fig. 12). In this system restoring particle size distribution
is easy, fast, and effective with minimal energy input.54 Redispersion
is achievable using gentle hand shaking rather than sonication
(sonication was required for the redispersion of most CO2-
switchable latexes reported in this review).
To decrease our dependence on petroleum feedstocks, polymers
derived from biomass offer an abundant and often inexpensive
alternative. Lignin, as the only biomass that contains aromatic
structures, has been used in the synthesis of a CO2-switchable
surfactant.108 The synthesized surfactant, lignin-g-DEAEMA, is
dispersible in water upon bubbling CO2 and coagulates upon
removal of CO2 by N2 bubbling.108 To demonstrate a potential
application of this CO2-switchable lignin compound, it was
employed as a surfactant for a Pickering emulsion.108 The
lignin-emulsified decane droplets were demulsified and redis-
persed by CO2 and N2 bubbling, respectively. The stabilization
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Table 3 Name, chemical structure, and related references for monomers

that have been used so far for the synthesis and preparation of CO2-
switchable (co)polymers
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pKaH pKaH
Name Structure (monomer) (homopolymer) Ref.

10, 35, 54, 88

DEAEMA 8.8 7.5
and 93–106

35, 37 and
DMAEMA 8.3 7.4
107–113

Fig. 12 Reversible coagulation/redispersion of an emulsion of dodecane

and water (dodecane 5 mL, SDS 0.20 g, and water 5 mL), the amount of
DMEA added to the emulsion was 1 mL.54 Reprinted from ref. 54 with DMAPMAm 9.2 8.8 132
permission from Wiley.

and destabilization processes were reversible and repeatable.

Also, the lignin materials were readily reclaimed and re-used in
the process.108 Stimuli-responsive Pickering emulsions including DMAPMA 9.1 8.4 132
CO2-responsive Pickering emulsions have been recently reviewed
by Tam and coworkers.109
A number of CO2-switchable amphipathic molecules were
synthesized by carbonyl-amine condensation reactions.110 The MA — — 14
emulsion stability of the latexes prepared using the synthesized
surfactants was also investigated. The best molar ratio of
dodecylamine and N,N-dimethylacetamide is 1 : 3 at 70 1C if
chloroform is used as solvent, and phosphorus trichloride as 3.3. CO2-switchable monomers
dehydrating agent and pH regulator. Also, it was found that the Table 3 shows monomers that have been used for the synthesis
stabilizing capacity of N 0 -hexadecyl-N,N-dimethylacetamidinium of CO2-responsive (co)polymers. DEAEMA and DMAEMA are the
bicarbonate is better than alternative options.110 two most studied CO2-switchable monomers, and have been used
Salentinig et al. studied the effect of the CO2-switchable extensively in the synthesis of pH-responsive polymers.112,121
amine groups on the behaviour of triblock copolymer micelles The polymeric tertiary amines are more hydrophobic in their
containing using small angle X-ray scattering technique.111 neutral form and more hydrophilic when the tertiary amine group
It was found that the amine groups interact with triblock becomes protonated to make the bicarbonate salt. This protonation
copolymer micelles and after protonation with CO2, the resulting and deprotonation can be performed reversibly by addition and
carbamate and bicarbonate anions alter the packing of polymer removal of CO2 (Fig. 13). The pKaH values of DEAEMA and the
chains. corresponding homopolymer are 8.8 and 7.5, respectively.132
One of the ongoing challenges with CO2-switchable surfactants is DEAEMA is a CO2-switchable monomer and therefore incorpor-
achieving precise control of the degree of protonation, which ating DEAEMA in the structure of (co)polymer can induce
depends on temperature, pKaH of the switchable groups, the local CO2-switchability to the whole polymer.61 DMAEMA is another
environment (e.g. particle surface) and effectiveness of the CO2
dispersion in the aqueous media. In some applications, this may
not be as critical but in other applications, for example emulsion
polymerization, it is a concern. In emulsion polymerization, the
amount of surfactant has a direct effect on the particle size and rate
of reaction. (More surfactant leads to a higher number of particles
with smaller size, increases the polymerization rate, and also allows
a higher solids content.) The particle size and solids content are both
important for end-use properties. When CO2-switchable surfactants
are used, only the protonated surfactant is effective, and therefore
controlling the degree of protonation becomes critical. Fig. 13 CO2-switchability of DEAEMA.

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CO2-switchable monomer having pKaH values of 8.3 and 7.4 for the
monomer and polymer, respectively.132 Although the chemical
structures of DEAEMA and DMAEMA are very similar, they have
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very different properties in terms of water-solubility. While DEAEMA

and PDEAEMA are hydrophobic, DMAEMA and PDMAEMA are
hydrophilic. With the same molecular weight, PDMAEMA can be
precipitated much more easily from hexane than PDEAEMA.70
While these two monomers are prone to hydrolysis,133 based on
our observations, at similar conditions of pH and temperature,
DEAEMA is more resistant to hydrolysis than DMAEMA. A good
substitute for these monomers is dimethylaminopropyl metha-
crylamide (DMAPMAm), which is a hydrophilic, CO2-switchable,
and hydrolytically stable monomer. The applications of these
monomers in the synthesis of CO2-switchable polymers will be
discussed in detail in Section 6 of this review.
Fig. 14 Preparation of a switchable polystyrene latex and its reversible
aggregation and redispersion triggered by removal and addition of CO2.11
3.4. CO2-switchable initiators
Reprinted from ref. 11 with permission from ACS publications.
0
2,2 -Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride (VA-044)
and 2,2 0 -azobis[2-(2-imidazolin-2-yl)propane] (VA-061) are two
important CO2-switchable initiators. To be more precise, VA-044 CO2-switchable latexes by emulsion polymerization because it
is CO2-switchable only after neutralization with a base to remove is not deprotonated as easily as those monomers at high
HCl. The 10 h half-life decomposition temperature of VA-061 is temperatures. However this could also be a disadvantage when
61 1C and decreases when protonated (B45 1C) which makes it complete switching off is desired. For some applications it may
suitable for initiating polymerizations under a CO2 atmosphere.11 be desirable to match as closely as possible the pKaH values of
Table 4 shows the structures of VA-061 and VA-044 and the the initiator-derived basic groups with those of the monomer.
references that have described the use of these initiators.
The positively charged imidazole groups resulting from 3.5. CO2-switchable solvents
decomposition of VA-044 or protonated VA-061 are very effective in
CO2-switchable solvents, meaning solvents that can switch back
stabilizing latex particles. The Cunningham and Jessop groups
and forth between two forms having contrasting properties,
performed surfactant-free emulsion polymerizations of styrene using
were developed to reduce the usage of volatile organic solvents.
VA-061 initiator under a CO2 atmosphere,11 finding that the latex
There are three classes of CO2 switchable solvents.
particles could be coagulated by CO2 removal and redispersed upon
3.5.1. Switchable polarity solvents (SPS). The first switch-
the introduction of CO2 (Fig. 14). The solid content was
able solvents, invented by the Jessop group, were CO2-triggered
relatively low (B7%), but could be increased if a small amount
switchable polarity solvents, which can reversibly change from
of a CO2-switchable comonomer was included.12 The high
a low-polarity form to a high-polarity form triggered by addition
temperature of the reactions (60–70 1C) leads to the deprotonation
of an atmosphere of CO2.134,135 If one step of a process requires
of the majority of the initiator which reduces the stabilizing effect
a low-polarity solvent and the next step requires a high-polarity
of the initiator. Based on our observations, by using VA-044 instead
solvent, then one would normally remove the solvent after the
of VA-061 under similar experimental conditions, PMMA latexes
first step and replace it with a second solvent suitable for the
with 20% solids content could be produced without using any
second step; but an SPS, in contrast, could be used for both steps.
comonomer or surfactant.
Therefore, the volume of solvent used in the process decreases.136
Since the pKaH of the amidine groups of VA-061 is larger
Because many solutes are much more soluble in one form of the
than monomers containing tertiary amines such as DEAEMA or
solvent than the other, switching the solvent can cause the
DMAEMA, it provides additional stability in the preparation of
precipitation of a product to occur. Amidine/alcohol mixes,134,135
guanidine/alcohol mixes,135 amidine/amine mixes,137–139 secondary
Table 4 Name, chemical structure, and related references of initiators amines,140 diamines,141 and guanidine/acidic alcohol mixes142 are
that have been used so far for the synthesis and preparation of CO2- some examples of SPS. These solvents can be employed as reaction
switchable (co)polymers
or extraction media.2,143–146,266 This leads to a reduction is
Name Structure Ref. the number of purification steps usually required in chemical
processes including polymerizations, and the solvent can be
1, 40, 45, 47, 54, recycled and re-used (Fig. 15).
VA-061
80–82 and 87 3.5.2. Switchable-hydrophilicity solvents (SHS). Another
important class of CO2-switchable solvents is switchable hydro-
VA-044 8–10 and 102 philicity solvents (SHS). These solvents can change from a hydro-
phobic state (forms a biphasic mixture when mixed with water)

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Fig. 15 The use of an SPS as the solvent for the polymerization of
styrene.2 Green and pink represent the low-polarity and high-polarity
forms of the SPS, respectively. Reproduced from ref. 2 with permission
from the RSC.
Fig. 16 The phase behaviour of a mixture of water and an SHS.147
Reproduced from ref. 147 with permission from the RSC.
to hydrophilic (miscible with water) when CO2 is added (Fig. 16).
Dozens of SHS are known; most of them are tertiary amines but
there are also some amidines and bulky secondary amines.147–181
Because distillation is not required for separating an SHS solvent
from a product, there is no need for an SHS to be volatile.147,156,182
SHS can be separated from a hydrophobic product by extraction
with carbonated water.2 After use, the solvent can be recovered
from the water by removal of CO2, which transforms the SHS to its
hydrophobic state and causes it to separate from the water.147 SHS
can be used in the recycling of polystyrene foam.156
3.5.3. CO2-switchable water. After water has been used as a
solvent, it is often expensive to separate from products because of
the high energy cost of distilling water. ‘‘Salting out’’ is a room
temperature method to separate dissolved solutes from water. In this
method, the ionic strength of an aqueous solution is increased by
addition of a salt. Because most organic solutes have little solubility
in an aqueous solution of high ionic strength, the addition of salt
triggers precipitation. This method is effective but not reversible and
still requires further treatment and significant energy costs to
remove the salt from the water so that the water can be reused.183
To address this problem, the concept of switchable water (SW), an
aqueous solution of switchable ionic strength, was invented by
Mercer and Jessop.183,184 Switchable water typically consists of an
aqueous solution of an ionogen, a compound which is not ionic but
that can be triggered to become ionic. Switchable water has potential
applications in viscosity switching, desalination, clay settling,
distillation-free recovery of water from wastewater,185,186 separation
4400 | Chem. Soc. Rev., 2016, 45, 4391--4436
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Chem Soc Rev
Fig. 17 (Top) An aqueous solution with CO2-switchable ionic strength:
‘‘switchable water’’. B is an amine or polyamine containing n sites basic
enough to be protonated by carbonated water.189 (Bottom) Illustration of
the use of switchable ionic strength water to reversibly expel an organic
compound from the aqueous phase. The change of the additive into a salt
raises the ionic strength of the water and forces out an organic product or
contaminant such as THF.183 Reprinted from ref. 189 and 183 with
permission from the RSC and Wiley, respectively.
and recycling of a catalyst,187 clay settling in mining extractions,130
and making conventional surfactants become CO2-switchable.54
For instance, when a CO2-switchable ionogen is in its neutral form,
the ionic strength of the aqueous solution is low, but after the
introduction of CO2, the ionic strength increases (Fig. 17 top).
Using a tertiary amine compound as a CO2-switchable additive,
THF can be separated from water by bubbling CO2 in the solution
and it can be dissolved again if CO2 is removed by bubbling of air
or N2 through the mixture (Fig. 17 bottom). To increase the
efficiency of the switchable ionogens, design and synthesis of these
materials should be performed based on specific principles.188
Switchable water is relevant to polymer chemistry in two ways;
the ionogen can be a polymer itself, or the switching of an ionogen
can be used to modify the behaviour of a polymer.
Recently it was shown that dimethylamino-functionalized
PMMA is a suitable polymeric ionogen for switchable water.189
Addition of CO2 protonates this polymer and causes settling of
fine clay particulates like kaolinite and montmorillonite. The
amino-functionalized PMMA with Mn of 120 kg mol1 was
particularly effective, increasing settling in the presence of
CO2 with polymer loadings as low as 10 ppm.189 Moreover, it
was shown by settling experiments and z-potential measure-
ments that the presence of CO2 is critical to attain coagulation
and flocculation when employing the polymer ionogens; the
polymer without CO2 had no effect.189
4. Synthesis of CO2-responsive
polymers
During the last decade, numerous research studies have been
published in the area of CO2-responsive polymers. A variety of
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Chem Soc Rev
polymers have been synthesized by different polymerization
techniques. In this section these techniques are reviewed in
detail.
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4.1. Free radical polymerization (FRP)
Free radical polymerization (FRP) is an important industrial
polymerization mechanism, and contains the three main steps
of initiation, propagation, and termination. FRP is widely used in a
variety of polymerization processes including bulk, solution, and
emulsion polymerization. For further details, the interested reader
is referred to the following ref. 73, 190 and 191. In the area of CO2-
switchable polymer latexes, mostly FRP has been employed for
preparing CO2-switchable latexes. The stability of the latex depends
on the degree of the protonation of the CO2-switchable compounds
in the latex. For long term stability, latexes should be kept under
a CO2 atmosphere, otherwise the latex particles gradually lose
their surface charge and due to the lack of sufficient electrostatic
repulsive forces, can eventually coagulate.
Fowler et al. reported the preparation of CO2-switchable PS
and PMMA latexes by FRP using the cationic switchable surfac-
tants (N 0 -hexadecyl-N,N-dimethylacetamidinium bicarbonate)
and (N 0 -dodecyl-N,N-dimethylacetamidinium bicarbonate).8 It
was shown that the aggregation behaviour of those latexes
depended largely on the amount of initiator, surfactant and
polymer concentration in the system. The first example of
redispersible CO2-switchable latexes was reported by Mihara
and coworkers.9 They showed that addition and removal of CO2
led to redispersion and coagulation of the latexes. To simplify the
process, PS CO2-switchable latexes were prepared using styrene
(monomer) and VA-061 (initiator) under CO2 atmosphere, without
added surfactant using what is known as ‘‘surfactant-free emulsion
polymerization’’.11 The initiator-derived endgroups on each poly-
mer chain, bearing an imidazole moiety, were protonated by CO2
and provided stabilization of the latex particles. However, since the
reaction temperature was relatively high (70 1C), most of the
imidazole groups created from initiator decomposition were likely
in their neutral form. Therefore, the total amount of charge
available for particle stabilization was limited, with the result being
the solid content could not be increased to more than B7%. The
produced latex was coagulatable and redispersible with removal
and addition of CO2, respectively. Addition of 0.54 mol% of
DEAEMA, as a CO2-switchable comonomer, led to a significant
increase in the achievable solids content to 27%.12 Adding a small
amount of MMA comonomer (B5 mol%) to the styrene emulsion
polymerization has a significant effect on the conversion as
it promotes particle nucleation. It was also realized that using
VA-044 as the initiator instead of VA-061 increased the charge
density (number of charges per unit surface area of each
particle). Since VA-044 is always fully protonated during the
polymerization while only a portion of VA-061 imidazole groups
are likely protonated under CO2, it was possible to produce
latexes with more than 20% solid content using only VA-044
without using any comonomer (unpublished data). The resulting
latex was CO2-switchable after neutralizing with a base. Zhu’s
group synthesized an amidine-containing styrene derivative
and employed it in the emulsion polymerization of styrene.192
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The resultant latex was coagulatable by adding a small amount
of NaOH and redispersible by CO2-bubbling. The same group
also synthesized a CO2-switchable reactive surfactant and used it for
the preparation of PS latex.101 However, the amidine group was
partially hydrolyzed during the polymerization. DEAEMA has been
used in the preparation of CO2-switchable Pickering emulsions.17,193
DEAEMA and DMAEMA are both prone to hydrolysis, specifically at
high temperatures and high pH. However, their corresponding
homopolymers are resistant to hydrolysis.133
CO2-switchable dextran-graft-poly((N-amidino)hexyl metha-
crylamide), (Dex-g-PAHMA), copolymers were prepared by FRP.194
Following synthesis of the monomer, (N-amido)hexyl methacryl-
amide (HMA), the FRP of HMA and dextran was performed in
aqueous solution using potassium persulfate initiator at 50 1C. The
product was purified by dialysis and the resulting solution
lyophilized to obtain purified copolymer.
Reversibly coagulating anionic latexes have also been prepared
using ‘‘switchable water’’.29 In the presence of N,N-dimethylethanol-
amine (DMEA) as a CO2-switchable additive, addition of CO2 leads to
the aggregation of the latex while subsequent removal of CO2 caused
redispersion of the latex and recovery of the original latex.
The studies reported to date have involved fairly low solid
content latexes (o30 wt%) while commercial processes are
typically run at >50 wt% polymer. A barrier for producing high
solid content latexes without using surfactant and only by
employing CO2 as a protonating agent is the limited solubility
of CO2 in water, especially at high temperatures usually used
for emulsion polymerization (>80 1C). Decreasing the tempera-
ture to increase the solubility of CO2 in the aqueous phase will
likely be required. Increasing the pressure is another option to
increase the CO2 concentration in the aqueous phase but would
require a pressurized reactor. Employing CO2-switchable com-
pounds with higher pKaH is another alternative, yielding higher
protonation efficiencies during polymerization but at the same
time resulting in more difficult coagulation of the latexes.
4.2. Reversible deactivation radical polymerization (RDRP)
In FRP, the lifetime of the growing chains is very short (less
than 1 second) and at the end of the reaction all of the polymer
chains are ‘‘dead’’. Therefore, the polymerization is not living
and block copolymers cannot be synthesized by this method.195
In anionic polymerization, developed by Szwarc,196 which in
principle is a true living system, chain transfer and termination
reactions are eliminated. This is only achievable by eliminating
all moisture and/or oxygen which requires high vacuum and
very low temperatures (B80 1C).197 However, by employing
RDRP (also known as living or controlled radical polymeriza-
tion), different monomers can be polymerized at milder con-
ditions typically employed in FRP while obtaining a relatively
high level of control over the polymer structures. Furthermore,
RDRP is not as sensitive to water as is anionic polymerization,
which is a key advantage because many industrial polymeriza-
tions are conducted in water (e.g. emulsion polymerizations for
producing latexes). In RDRP, since irreversible termination
reactions are minimal, chains are living for a longer period of
time (ideally for the entire polymerization) and it is possible to
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add a second (or even third) block in order to prepare block

copolymers.195 As will be seen in subsequent sections, RDRP
has become the polymerization technique of choice for preparing
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CO2-switchable polymers with a complex or sophisticated micro-

structure or mesostructure, including for example di- and triblock
copolymers and nanostructured particles. FRP, being simpler and
less expensive than RDRP, remains a suitable choice when precise
control of the molecular weight distribution is not required and
more complex molecular architectures are unnecessary.
The three most common types of RDRP are: nitroxide mediated
polymerization (NMP), atom transfer radical polymerization (ATRP),
and reversible addition fragmentation transfer (RAFT) polymeriza-
tion. The main difference between RDRP and FRP is that in RDRP
Fig. 19 Synthetic route of diblock copolymer PEO-b-PAD via ATRP.29
the termination reactions are reduced considerably by addition of a
Reproduced from ref. 29 with permission from Wiley.
control agent in the reaction to promote the reversible deactivation
of propagating chains. For example, in NMP a nitroxide is added to
the system to deactivate propagating radicals and minimize mutual temperature and the polymer had low molar mass dispersity
termination. In ATRP, a transition metal catalyst is used while in (Ð = 1.14), showing good control over the course of the poly-
RAFT a chain transfer agent is responsible for reducing the merization.29 Fig. 19 shows the synthesis route for preparing
frequency of termination reactions. NMP and ATRP are based on PEO-b-PAD. The reaction was carried out in anhydrous methanol
reversible termination while RAFT is based on reversible chain for 12 h using pentamethyldiethylenetriamine (PMDETA) as
transfer.198 Each of these controlling mechanisms can produce a ligand and copper bromide (CuBr) as catalyst.
polymer with a low dispersity (Ð o 1.5). Comprehensive reviews Using the same ligand, PMDETA, the CO2-switchable triblock
of RDRP in different polymerization systems including dispersed copolymer PEO-b-PS-b-PDEAEMA (OSA) was prepared by ATRP.31
systems have been published.195,197–202 For the preparation of the PEO macroinitiator, the ATRP of
Applying RDRP techniques for producing switchable materials is mono-methoxyl poly(ethylene oxide) was conducted in dichloro-
becoming an active area of research. The synthesis of CO2-switchable methane (CH2Cl2) in the presence of triethylamine (TEA) at room
polymers using RDRP is highlighted in the following sections. temperature for 24 h using 2-bromo-isobutyryl bromide (BiBB) as
4.2.1. Atom transfer radical polymerization (ATRP). In ATRP, initiator. The macroinitiator (O–Br) then was employed in the
an equilibrium exists between propagating radicals and dormant ATRP of styrene in bulk using copper bromide (CuBr) catalyst
species.203 The dormant species (Pn–X) are predominant and and PMDETA ligand (Fig. 20). The reaction continued for 16 h at
periodically react with transition metal complexes. Transition 110 1C to obtain OS macroinitiator for the third step. In the last
metal complexes act as activators in their lower oxidation state step, ATRP of DEAEMA was carried out in toluene using OS
(Mtm/L), reacting with halide terminated ‘‘dormant’’ chains to macroinitiator, a mixture of copper chlorides (CuCl and CuCl2)
give propagating radicals (Pn ) and transition metal complexes in catalyst, and PMDETA ligand at 60 1C for 24 h. Also, PMDETA
their higher oxidation state. In their higher oxidation state, the ligand was employed in the synthesis of a PDMAEMA-b-PEO-b-
transition metal complexes are coordinated with halide ligands PDMAEMA triblock copolymer as a CO2-switchable nanocomposite
(X–Mtm+1/L) and act as deactivators. The deactivator reacts with by ATRP using Br–PEO–Br initiator.205
propagating radicals to yield dormant species and the activator A fluorophore–polymer conjugate, PBI–PDMAEMA, com-
(Fig. 18). Therefore, the concentration of propagating radicals is prised of two CO2-switchable arms of PDMAEMA and a centre
kept low (compared to FRP) and termination reactions are
reduced.204 Removal of the transition metal catalyst and ligand
may be required for some applications. This is straightforward
for homogeneous systems but can be more difficult in hetero-
geneous systems.
Poly(ethylene oxide)-b-poly((N-amidino)dodecyl acrylamide),
PEO-b-PAD, was synthesized by ATRP.29 Since the second
block contained amidine groups, the diblock copolymer was
CO2-switchable (Fig. 19). The ATRP was performed at room

Fig. 20 Synthetic route for the triblock copolymer poly(ethylene oxide)-

block-polystyrene-block-poly(N,N-diethylamino ethyl methacrylate) (OSA)
Fig. 18 ATRP equilibrium.204 Reproduced from ref. 204 with permission via a sequential ATRP protocol.31 Reproduced from ref. 31 with permission
from ACS publications. from ACS publications.

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Fig. 21 Synthesis route of PBI-containing PDMAEMA and the reaction of
PDMAEMA with CO2.20 Reproduced from ref. 20 with permission from the RSC.
perylene-3,4,9,10-tetracarboxylic acid bisimide (PBI) fluorophore,
was synthesized via the ATRP of DMAEMA from the N,N 0 -bis{2-
[2-[(2-bromo-2-methylpropanoyl)oxy]ethoxy]ethyl}perylene-3,4,9,10-
tetracarboxylic acid bisimide initiators.20 After synthesizing PBI–Br
macroinitiator (ATRP macroinitiator), it was employed in the ATRP
of DMAEMA using CuBr as catalyst, PMDETA as ligand, and THF
as solvent (Fig. 21).
Hybrid nanoparticles consisting of a PDEAEMA shell and
fluorescence-labelled magnetic cores were synthesized by a two-step
ATRP.115 In the first step magnetic nanoparticles were prepared and
2-bromopropionyl bromide was used to attach the bromide onto the
surface of the nanoparticles. Then, the macroinitiator was employed
in the ATRP of DEAEMA using CuBr catalyst and PMDETA
ligand to modify the surface of the magnetic nanoparticles with
CO2-switchable PDEAEMA brushes.
Zhu’s group reported the synthesis of double O2- and CO2-
responsive diblock copolymer comprised of poly(ethylene oxide) as
the hydrophilic block and poly((diethylamino)ethyl methacrylate-
co-trifluoroethyl methacrylate) as a dual responsive block.119 The
diblock copolymer was prepared by the ATRP of DEAEMA and
2,2,2-trifluoroethyl methacrylate (FMA), (mole ratio of DEAEMA to
FMA was 2), using PEG–Br as macroinitiator, CuBr as a catalyst,
and 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) as
a ligand. In a similar work, the same group produced a O2- and
N2-responsive FMA–DMAEMA copolymer via ATRP (Fig. 22).206
CO2-switchable polymeric microtubules, which can be self-
assembled in different sizes and morphologies depends on time
of the CO2 stimulation were also made by ATRP.207 The triblock
poly(ethylene oxide)-block-poly(N-amidine)dodecylacrylamide-
block-poly(styrene) copolymer was synthesized by sequential
Fig. 22 Synthesis of poly(DMAEMA-co-FMA).206 Reproduced from ref. 206
with permission from Wiley.
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Fig. 23 Synthetic route for the triblock copolymer poly(ethylene
oxide)-block-poly(n-amidine)dodecylacrylamide-block-polystyrene (EAS) via
sequential ATRP.207 Reproduced from ref. 207 with permission from Wiley.
ATRP (Fig. 23). First, PEO macroinitiator was prepared using
mono-methoxyl poly(ethylene oxide) monomer, 2-bromo-isobutyryl
bromide (BiBB) initiator, and then PEO–Br macroinitiator was
employed in the ATRP of (N-amidino)dodecylacrylamide using
CuBr catalyst and PMDETA ligand and finally the product was
employed in the ATRP of styrene.207
We prepared a CO2-switchable four-armed star-like hydro-
phobic associative polymer comprised of a water-soluble poly-
acrylamide core and PDEAEMA arms, (PAM60–PDEAEMA20)4,
via ATRP.120 First, a four-armed initiator was synthesized by the
reaction between BiBB and; this was then used to initiate the ATRP
of acrylamide with CuBr and 2,20 -bipyridine (bpy). DEAEMA was
then added to the flask and the reaction continued for another
24 h.120 DMAEMA has also been used in the preparation of CO2-
switchable hydrophobic associative polymers.208 The solutions of
the copolymers of poly(acrylamide)-co-poly(DMAEMA)-co-poly(N-
cetyl DMAEMA) exhibited a pronounced CO2-switchable viscosity
response.208 In the absence of CO2, the chains associate with each
other strongly due to hydrophobic interactions, while when CO2 is
present, the hydrophobic associations are weakened by the charged
groups on the polymer. Viscosity increases by approximately four
orders of magnitude when CO2 was replaced with Ar, and this affect
can be slightly enhanced by the presence of salt which acts to
further screen the charges.
CO2-switchable polymer brushes were synthesized via surface-
initiated ATRP for reversible adsorption (in extended or hydrated
form) and desorption (in collapsed or dehydrated form) of
protein.116 After preparing the initiator substrate, it was employed
to initiate the surface ATRP of DEAEMA in methanol using CuBr
and PMDETA (Fig. 24).
A CO2-switchable liposoluble star copolymer containing
PDMAEMA arms and hyperbranched polyethylene (HBPE) core
showed fast micellization after dispersion in water and treatment
with CO2.127 For the synthesis of this copolymer, in the first step the
core of the star copolymer was prepared via ethylene chain walking
copolymerization (CWP) and then it was used as a macroinitiator in
the ATRP of the DMAEMA in the presence of CuCl/CuCl2 and
1,1,4,7,10,10-hexamethyltriethylene-tetramine (HMTETA) (Fig. 25).
Yuan et al. synthesized the dual responsive triblock copolymer
PNIPAM-b-PCL-b-PDMAEMA using different polymerization
techniques.125 For synthesizing the PDMAEMA block, ATRP
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Fig. 24 Synthesis of surface-initiated ATRP of PDEAEMA brush.116 Reproduced

from ref. 116 with permission from the RSC.

Fig. 25 Synthesis of HBPE–PDMAEMA stars by a Pd-catalyzed chain walking

copolymerization of ethylene and 2-(2-bromoisobutyryloxy)ethyl acrylate
followed by an atom-transfer radical copolymerization of DMAEMA.127
Reproduced from ref. 127 with permission from ICE publishing.

was performed using CuBr as catalyst, PMDETA as ligand, and

b-cyclodextrin (b-CD)-based ATRP initiator (b-CD–Br) (Fig. 26).
Water-soluble lignin was prepared via ATRP grafting of
DEAEMA.108 First a lignin–Br ATRP macroinitiator was synthe- Fig. 27 Synthesis of lignin-g-DEAEMA via ATRP of DEAEMA.108 Reprinted
from ref. 108 with permission from the RSC.
sized and then employed in the ATRP of DEAEMA (Fig. 27).108
A CO2-switchable polymeric film was grown on the surface of
a nascent membrane via surface-initiated ATRP.209 To perform
the reaction, 2-bromopropionyl bromide was coupled via to the
PEI coated membrane surface and it was then employed for the
polymerization of DEAEMA.
Surface-initiated ATRP (SI-ATRP) was employed in the synthesis
of a CO2-switchable drying agent containing tertiary amine
groups.131 For the preparation of the drying agent, PDMAPMAm
was grafted to the surface of the silica-functionalized particles using
BiBB initiator (Fig. 28).
The diverse range of CO2-switchable polymers, especially
block copolymers, made by ATRP described in the above section,
and the broad scope of intended applications, is attributable to the Fig. 28 Synthesis of CO2-switchable drying agent by SI-ATRP using
silica-functionalized particles.131 Reprinted from ref. 131 with permission
ease of using ATRP to make complex morphologies, its suitability
from the RSC.
for surface-initiated polymerizations, and its wide applicability to a
range of monomers. It should be noted that amine-bearing mono-
mers may be problematic for some ATRP reactions, as the mono-
mers can compete with the ligand resulting in poor control and/or lower reaction rate. Appropriate selection of the ligand and reaction
conditions becomes particularly important if this is a concern.
4.2.2. Reversible addition–fragmentation chain-transfer (RAFT)
polymerization. A typical RAFT polymerization kinetic scheme is
shown in Fig. 29.210 Briefly, reaction I is the initiation step in RAFT,
which is similar to FRP. In the pre-equilibrium step (reaction II), the
transfer of RAFT agent to a propagating chain to yield a macroRAFT
Fig. 26 Synthesis route for b-CD–PDMAEMA.125 Reprinted from ref. 125 agent occurs. Reaction IV represents the main RAFT-equilibrium,
with permission from ACS publications. whereby the RAFT agent is transferred between growing polymer

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Fig. 29 Scheme illustrating the RAFT mechanism.210 Reprinted from
ref. 210 with permission from Wiley.
chains. Propagation (reaction III) and termination (reaction V) also
occur similar to the FRP mechanism.210
Since RAFT is amenable to a wider variety of monomers than
either NMP or ATRP, this technique has been used frequently
in the synthesis of well-defined (co)polymers with narrow
molecular weight distribution and targeted-end functionalities.
The RAFT agent can impart colour to the product and residual
odour may also be an issue, requiring post-reaction removal of
the RAFT agent from the polymer chain ends.
RAFT has been also employed successfully in the synthesis of
CO2-switchable polymers. A dual CO2- and temperature-responsive
block copolymer, PDEAEMA-b-PNIPAM, was synthesized with RAFT
polymerization.28 For the preparation of the first block RAFT
polymerization of DEAEMA was performed using 2,2-azobis (iso-
butyronitrile) (AIBN) initiator and 2-dodecylsulfanylthiocarbonyl-
sulfanyl-2-methyl propionic acid (DMP) RAFT agent at a molar
ratio of 1 : 10. This macroRAFT agent was then used in a chain
extension with NIPAM, which is thermoresponsive (thus yield-
ing a dual responsive polymer) (Fig. 30). In the synthesis of the
second block, AIBN was again used as initiator with a molar
ratio of 1 : 10 with respect to PDEAEMA–CTA macro-initiator.28
Poly(4-chloromethylstyrene) (PCMS) was prepared by RAFT
polymerization and then employed as a precursor for the synthesis
of a CO2-switchable amidine-based polymer.211 In this work, PCMS
was prepared by RAFT polymerization of 4-chloromethylstyrene
(CMS) and then PCMS was post-modified into poly(p-azidomethyl-
styrene) (PAMS) by replacement of the chloro groups with azido
units. By then employing a Cu(I)-catalyzed cycloaddition click
reaction, azido units were coupled with N 0 -propargyl-N,N-
dimethylacetamidine (PDAA) moieties to obtain the final
amidine-based polymer (Fig. 31).
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Fig. 30 Synthetic route for the diblock copolymer poly[N,N-diethyl-
aminoethyl methacrylate-block-(N-isopropylacrylamide)] (PDEAEMA-b-
PNIPAM) via sequential RAFT.28 Reproduced from ref. 28 with permission
from the RSC.
Fig. 31 Synthesis of an amidine-based polymer and its reaction with CO2
and water.211 Reproduced from ref. 211 with permission from the RSC.
RAFT polymerization has also been combined with click
chemistry for the preparation of CO2-switchable single-walled
carbon nanotubes (SWCNTs).212 Using RAFT, the precursor
PCMS was synthesized and post-modified to get poly( p-azidomethyl-
styrene) (PAMS). For preparing the PCMS, RAFT polymerization
of 4-chloromethylstyrene was performed in anisole using AIBN
initiator and S-1-dodecyl-S 0 -(a,a 0 -dimethyl-a00 -acetic acid)-tri-
thiocarbonate (DDMAT) RAFT agent.
Two types of CO2-responsive diblock copolymer, PEO-b-
(DEAEMA-r-S) and PEO-b-DEAEMA-b-S, were synthesized by
RAFT polymerization to explore the effect of the distribution of
DEAEMA in the morphological transition in aqueous solution.114
An ester condensation reaction was used for the preparation of
macroRAFT agent using 4-cyano-4-thiothiopropylsulfanylpentanoic
acid (CTPPA) RAFT agent in the presence of 4-(dimethylamino)-
pyridine (DMAP) and N-(3-dimethylaminopropyl)-N 0 -ethylcarbo-
diimide hydrochloride crystalline (EDAC). This macroRAFT
agent was further used in the synthesis of the two different
block copolymers (Fig. 32).
A CO2-switchable triblock copolymer with a segregated
corona has also been synthesized via a two-step RAFT polymeriza-
tion, underscoring the usefulness of RDRP for making structured
morphologies.117 The PEO macroRAFT agent was synthesized using
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Fig. 32 Synthesis route of PEO-b-DEAEMA-b-S and PEO-b-(DEAEMA-r-S).114
Reproduced from ref. 114 with permission from the RSC.
poly(ethylene glycol) methyl ether (mPEG-5000, Mn B 5000 g mol1)
monomer. The macroRAFT agent was employed in the RAFT
polymerization of 2,2,3,4,4,4-hexafluorobutyl methacrylate (HFBMA)
monomer using 4,4-azobis(4-cyanopentanoic acid) (ACPA) initiator
(molar ratio of initiator to macroRAFT agent was 0.2 : 1). The product
was then used in the RAFT polymerization of DEAEMA to produce
triblock copolymer. A similar triblock copolymer was synthesized
by RAFT polymerization to study the morphological changes by
variation of water ratio in the water/ethanol mixed solvent.213
Zhao and coworkers61 synthesized a library of CO2-switchable
diblock copolymers containing DEAEMA or DMAEMA via
RAFT polymerization. In most cases AIBN was used as initiator,
2-(2-cyanopropyl)dithiobenzoate (CPDB) as RAFT agent, and dioxane
as solvent. The same group also prepared CO2-switchable recyclable
gold nanoparticles (AuNPs).118 First, gold nanoparticles and thiol-
terminated PDEAEMA (SH-PDEAEMA) were prepared separately.
Then gold nanoparticles were functionalized with PDEAEMA.
For the synthesis of SH-DEAEMA, RAFT polymerization of
DEAEMA was conducted using AIBN as initiator and CPDB as
RAFT agent. This group also demonstrated a general strategy
for making CO2-switchable vesicles.113 A macroRAFT agent was
prepared by the RAFT polymerization of dimethacrylamide (DMA)
using AIBN and CPDB. Chain extension was then performed by
polymerizing the DEAEMA block.
Poly(pentafluorophenyl acrylate) (PPFPA) homopolymer,
PPFPA-b-PDMA, and PPFPA-b-PEGA diblock copolymers were
prepared by RAFT.66 To induce CO2-switchability in these polymers,
the PFPA homopolymers were functionalized with histamine (HIS)
dihydrochloride and L-arginine methyl ester (ARG) dihydrochloride
(commercially available amidine and guanidine species) in the
presence of S-methyl methanethiosulfonate to obtain the corres-
ponding amidine and guanidine-based acrylamido polymers
(Fig. 33). The HIS and ARG homopolymers are CO2-switchable.
Also, PPFPA-b-PDMA and PPEGA-b-PPFPA diblock copolymers
with a range of molar compositions were synthesized by RAFT
and these precursor polymers were converted to the corres-
ponding HIS and ARG block copolymers.66 It was demonstrated
that the DMA–HIS and PEGA–HIS diblock copolymers were able
to self-assemble reversibly in aqueous media upon alternatively
treating with CO2 and N2.
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Fig. 33 Synthetic route for the preparation of homopolymers containing
amidine and guanidine functionality via post-polymerization modification
of PPFPA with histamine and L-arginine methyl ester (top), and synthetic
route for the preparation of PPFPA-b-PDMA and PEGA-b-PPFPA (bottom).66
Adapted from ref. 66 with permission from Wiley.
CO2-switchable diblock copolymers comprised of PMMA as
the hydrophobic block and PDMAEMA as the CO2-responsive block
were synthesized by a two-step solution RAFT polymerization
and employed as the surfactant in emulsion polymerization of
MMA.77,101 In the first step, the RAFT polymerization of DEAEMA
was conducted using AIBN as the initiator and 2-cyanopropan-
2-yl dodecyl trithiocarbonate (CPDTTC) as the RAFT agent. Then
a deoxygenated solution of MMA in dioxane with AIBN was
added to the flask and the reaction continued for additional
9 h at 70 1C (Fig. 34).
RAFT polymerization of poly(pentafluorophenyl acrylate)
(PPFPA) was performed using AIBN initiator and benzyl benzo-
dithioate RAFT agent and the resulting macroRAFT agent was
employed in the polymerization of different diblock copolymers
containing NIPAM as a temperature-sensitive monomer and
L-arginine as a CO2-switchable monomer to obtain dual temperature
and CO2-responsive polymers.129 RAFT has also been employed for
the synthesis of the PNIPAM block in the CO2-switchable triblock
copolymer PNIPAM-b-PCL-b-PDMAEMA (Fig. 35).125
Fig. 34 Synthesis route of PDMAEMA-b-PMMA block copolymers.77
Reproduced from ref. 77 with permission from ACS publications.
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Fig. 35 Synthesis route for CTA–PNIPAM.125 Reproduced from ref. 125
with permission from ACS publications.
Fig. 36 Synthesis of PDMAEMA-b-PS via surfactant-free miniemulsion
RAFT polymerization.126 Reproduced from ref. 126 with permission from
Elsevier.
CO2-switchable PDMAEMA-b-PS nanoparticles were prepared
via surfactant-free miniemulsion RAFT polymerization.126 For the
preparation of the PDMAEMA block, the RAFT polymerization of
DMAEMA was performed in bulk and then the PDMAEMA
macroRAFT agent was used in the miniemulsion polymerization
of styrene (Fig. 36).
A dual temperature and CO2-switchable polymer was synthesized
by RAFT polymerization of 3-(2-(diethylamino)ethylamino)–
N-isopropylpropanamide–acrylamide (DEAE–NIPAM–AM).214 The
monomer was not available commercially and had to be synthesized
(Fig. 37). After synthesizing the monomer it was employed in the
RAFT polymerization using AIBN and S,S0 -bis(a,a0 -dimethyl-a00 -acetic
acid)trithiocarbonate (BDMAT) as the RAFT agent.214
Dual responsive poly(oligo(ethylene glycol)methyl ether metha-
crylate)-block-poly(N,N-diethylaminoethyl methacrylate)-block-poly-
(2-(3-(2-aminophenyl)-ureido)ethyl methacrylate) (POEGMA-b-
PDEAEMA-b-PAPUEMA) triblock copolymer (named ‘‘ODA’’)
was synthesized by sequential RAFT polymerization.215 In the
Fig. 37 Poly(DEAE–NIPAM–AM).214 Reproduced from ref. 214 with
permission from ACS publications.
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Fig. 38 Design strategy of poly(MEOn–DEAE–AM) homopolymers.216
Reproduced from ref. 216 with permission from Elsevier.
first step, POEGMA macroRAFT agent was prepared via the
RAFT polymerization of OEGMA monomer employing CPBD as
RAFT agent and AIBN as initiator. The macroRAFT agent was then
used in the polymerization of DEAEMA. Finally the OD diblock
copolymer was used as a macroRAFT agent in the synthesis of ODA
triblock copolymer via polymerization of APUEMA.
A new monomer bearing oligo(ethylene glycol) units and a
diethylamino ethyl group was designed for RAFT polymerization to
produce the corresponding homopolymer, which was dually tem-
perature and CO2-responsive.216 The monomer was synthesized via
an aza-Michael addition reaction and subsequent amidation with
acryloyl chloride. Oligo(ethylene glycol), N,N-diethylaminoethyl, and
polymerizable double bonds were connected to each other by amino
group. Then RAFT polymerization of the synthesized monomer was
performed using AIBN and CTA RAFT agent (Fig. 38).
RAFT polymerization was used as the last step in the
preparation of dually responsive poly(3-aprolactone)-block-poly-
(N-isopropylacrylamide-co-N,N-dimethylaminoethyl methacrylate)
terminated with a pyrene containing group (Py-PCL-b-P(NIPAM-
co-DMAEMA)).217 In the first step Py-PCL was synthesized
by ring-opening polymerization (ROP), and then reacted with
S-dodecyl-S0 -(a,a0 -dimethyl-a00 -acetic acid)trithiocarbonate (DDMAT)
to produce Py-PCL–DDMAT. This product was employed as the
macroRAFT agent in the polymerization of NIPAM and DMAEMA
using AIBN in dioxane solvent (Fig. 39).
Dual responsive PADS-b-PDMAEMA diblock copolymer contain-
ing amidine and dimethylamino ethyl groups was synthesized by
the combination of RAFT polymerization and click chemistry.218
First, poly(p-chloromethylstyrene) (PCMS) was prepared via RAFT
polymerization using DDMAT as the RAFT agent and AIBN in
anisole solvent. Polymerization continued for 24 h at 70 1C.
The synthesized PCMS was dissolved in dry DMF and reacted with
NaN3 to produce PAMS. Then, PAMS was used as the macroRAFT
agent for the polymerization of DMAEMA in the preparation of
PAMS-b-PDMAEMA. Eventually, N 0 -propargyl-N,N-dimethylacet-
amidine (PDAA) and PAMS-b-PDMAEMA were dissolved in dry
DMF in the presence of CuBr and PMDETA and the click
reaction continued for 12 h at 50 1C to produce PADS-b-
PDMAEMA (Fig. 40).
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Fig. 39 Synthesis of amphiphilic block copolymer Py-PCL-b-P(NIPAM-
co-DMAEMA).217 Adapted from ref. 217 with permission from the RSC.
Fig. 40 Synthesis of the PADS-b-PDMAEMA copolymer.218 Reproduced
from ref. 218 with permission from the RSC.
PEO113-b-P(4VP90-r-DEAEMA30) CO2-switchable block copolymer
was prepared via RAFT polymerization.123 PEO macroRAFT
agent was synthesized using CTPPA RAFT agent and then it
was employed in the chain extension with DEAEMA and 4VP
monomers (Fig. 41).
As shown above, RAFT has been used to polymerize a wide
range of monomers and prepare numerous different types of
CO2-switchable polymeric structures. While it is versatile, selection
of the RAFT agent is critical, and synthesis of block copolymers
can be a challenge if the selected RAFT agent is not suitable for
each of the blocks. RAFT, like NMP (see below), is well suited to
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Fig. 41 The synthesis pathway of the block-random segmented polymer
PEO113-b-P(4VP90-r-DEAEMA30).123 Reproduced from ref. 123 with
permission from the RSC.
emulsion/miniemulsion polymerizations and typically does not
require special conditions relative to solution/bulk polymerization.
By comparison ATRP emulsion/miniemulsion use of requires highly
hydrophobic ligands to restrict the catalyst to the polymer particles
and minimize catalyst partitioning into the aqueous phase.
4.2.3. Nitroxide-mediated polymerization (NMP). In the
1980s, Solomon et al. discovered that radicals generated in free
radical polymerization can be trapped by nitroxides and lead to
controlled and living low molecular weight polymers.219 In 1993,
Georges and coworkers220 used 2,2,6,6-tetramethylpiperidinyl-N-
oxyl (TEMPO) as a nitroxide in the living radical polymerization
of styrene and produced polystyrene with a narrow molecular
weight distribution. This work became the foundation of
nitroxide-mediated polymerization. In NMP, an alkoxyamine is
decomposed homolytically and generates nitroxide and initiator
radicals (Fig. 42).221
Nitroxides are stable radicals that usually do not self-
terminate but are able to react with propagating radicals and
deactivate them. Activation of a nitroxide-terminated polymer
chain occurs approximately every 102 to 103 seconds while
deactivation takes place very fast (B103 s). However, during
Fig. 42 Reversible activation and deactivation in NMP.221 Reproduced
from ref. 221 with permission from the RSC.
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the short period time of between activation and deactivation, a
few monomers (typically 1 to 5) are added to the growing
chains,197 yielding polymer with a narrow molecular weight
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distribution (MWD). Nitroxides do not undergo irreversible
termination reactions, but propagating radicals can terminate
with each other. As conversion increases, limited irreversible
termination does occur and the ratio of nitroxide radicals to
propagating radicals increases. Since alkoxyamines are usually
activated at elevated temperatures (>90 1C), applying NMP for the
synthesis of CO2-switchable polymers under CO2 atmosphere
(where the CO2-switchable monomers are in their protonated
form) is not possible unless high pressures are applied to maintain
a sufficiently high dissolved CO2 concentration. Alternatively the
CO2-switchable functional groups can be protonated by strong acids
such as HCl, however the resulting polymers are not CO2-switchable
unless the strong acid is neutralized with base, preferably followed
by washing to remove residual salt. However, well-defined CO2-
switchable polymers can be synthesized via NMP under N2. For
example, Zhou et al.222 prepared poly(p-chloromethylstyrene)-
co-polystyrene (PCMS-co-PS) with low molar dispersity using
NMP and then post-modified the polymer into poly(p-azido-
methylstyrene)-co-polystyrene (PAMS-co-PS) before introducing
amidine groups into the PAMS-co-PS using the Staudinger liga-
tion. The obtained polymer could undergo a neutral-charged-
neutral transition in DMF containing 0.5% H2O by alternatively
bubbling CO2 and N2 through the solution (Fig. 43). Such a
reversible transition was confirmed by sharp conductivity varia-
tion of the polymer.222
Recently our group reported the preparation of PDEAEMA
via NMP.70,133 Poly(DEAEMA-co-S) was synthesized by NMP and
then employed as a macroalkoxyamine in the emulsion poly-
merization of MMA (Fig. 44).70 The macroalkoxyamine was
CO2-switchable, which was confirmed by bubbling CO2 through
its aqueous solution (Fig. 45).
Fig. 43 Reversible deprotonation of p(‘‘amidine’’MS)-co-PS in DMF with
0.5% H2O after alternating bubbling of CO2 and N2.222 Reproduced from
ref. 222 with permission from ACS publications.
Fig. 44 Synthesis of poly(DEAEMA-co-S) macroalkoxyamine.47
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Fig. 45 CO2-switchability test of the poly(DEAEMA-co-S): (a) in methanol
(b) after adding water (c) after bubbling CO2 for 10 minutes at room
temperature.70
In summary, any RDRP technique can be suitable for preparing
CO2-responsive polymers. It is commonly believed that when using
RDRP it is important to have excellent control of the molar mass
dispersity (e.g. Ð o 1.15) but we dispute this notion. The require-
ment for low dispersity is highly application dependent. A few
applications may indeed require very narrow molecular weight
distributions (possibly for all blocks in a block copolymer) but in
our experience satisfactory performance can often be achieved with
relatively broad distributions (e.g. Ð > 1.5), provided most or all of
the polymer chains have the desired structure, for example a di- or
triblock polymer.
4.3. Postpolymerization modification
Combinations of different methods of polymerization and post-
polymerization modifications have been used to prepare poly-
mers with desired functionality. However, few reports are yet
available related to postpolymerization modification for synthe-
sizing CO2-switchable polymers. We believe this will change
rapidly in coming years as the versatility of CO2-switchable
polymers becomes better appreciated. Postpolymerization
modification will be best suited when a monomer required to
make a polymer is not available, or sufficiently reactive or
stable. Functionalization of polymers is often difficult and
may not be quantitative. Poly(4-chloromethylstyrene) (PCMS)
was first prepared via RAFT polymerization, post-modified into
reactive poly(p-azidomethylstyrene) (PAMS) and finally coupled
with N 0 -propargyl-N,N-dimethylacetamidines (PDAA) via a click
reaction.211 CO2-switchable SWNTs were synthesized by first
preparing N0 -propargyl-N,N-dimethylacetamidines (PDAA), N-(prop-
2-ynyl)-4-(pyren-1-yl)butanamide (PPBA), and poly(4-chloromethyl-
styrene) (PCMS). PCMS was further post-modified to poly-
( p-azidomethylstyrene) (PAMS). Eventually PDAA and PPBA were
clicked onto PAMA to obtain pyrene-labelled amidine-based poly-
mers.212 CO2-switchable homo and block copolymers containing
histamine and L-arginine were prepared via post-polymerization
modification of poly(pentafluorophenyl acrylate) homopolymers.66
Porous polymer networks (PPNs) were modified with different
amine compounds to increase CO2-uptake capacities.22 It was
observed that CO2-uptake capacities increase in the order of:
diethylenediamine (DETA) > tris(2-aminoethyl)amine (TAEA) >
triethylenetetramine (TETA) > ethylenediamine (EDA). Also, it
has been shown that PPN-6-CH2DETA, an amine-grafted porous
polymer network, has a very high CO2-uptake capacity.23
The Theato group129 prepared PPFPA via RAFT polymeriza-
tion and then attached the temperature responsive monomer
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Fig. 46 Synthetic strategy of the temperature- and CO2 responsive
polymers PI, PII and PIII. For clarity reasons the CTA group is not shown.129
Reproduced from ref. 129 with permission from Elsevier.
(NIPAM) and CO2-responsive monomer (L-arginine) by post
polymerization modification to prepare dually responsive poly-
mers (Fig. 46).
5. Self-assembly of CO2-responsive
polymers
One of the most exciting features of CO2-responsive polymers is
their reversible self-assembly in aqueous media. One advantage
of the CO2 trigger is biocompatibility that makes CO2-switchable
polymers potential candidates for biomedical applications. Also,
CO2 does not accumulate in the system and thus addition and
removal of CO2 can be done without concern for the accumula-
tion of salt or other chemicals. As will be seen in this section,
CO2-switchability has been used as the driving force to create
not only new polymer microstructures (such as diblocks and
triblocks), but also CO2-responsive nanostructured materials. An
incredibly diverse range of new structures has been created in
the past few years. We anticipate that in the coming decade
applications will be discovered for some of these new structures,
or they will serve as inspiration for further modifications to serve
new applications. Many of these structures require the use of the
RDRP techniques described previously.
5.1. Self-assembly of polymers containing DEAEMA
DEAEMA is hydrophobic in its neutral form and hydrophilic in its
protonated form, and is readily CO2-switchable in aqueous solution,
leading to interesting applications in the synthesis of polymers that
can self-assemble using CO2 as a trigger. For example, PDMA-b-
PDEAMA diblock copolymer nanoparticles are converted to free
polymer chains after treating with CO2 as a result of DEAEMA
protonation.113 However, in a similar diblock copolymer with a
PEO hydrophilic block, if the DEAEMA block is crosslinked with
coumarin methacrylate (CMA) comonomer, the complete dissocia-
tion of the vesicles is not possible and only volume expansion occurs
because of the electrostatic repulsion forces between positively-
charged the tertiary amine groups. Upon deprotonation by removal
of CO2, vesicles return to their original size (Fig. 47).
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Fig. 47 Illustration of CO2-switchability of: (a) PDMA-b-PDEAEMA (b) PEO-b-
P(DEAEMA-co-CMA).113 Reprinted from ref. 113 with permission from the RSC.
DEAEMA has also been employed in the synthesis of a CO2-
switchable triblock copolymer comprised of an outer hydro-
philic PEO block, a middle hydrophobic PS bridging block, and
a CO2-responsive interior PDEAEMA block (PEO-b-PS-b-PDEAEMA).31
Depending on the composition of the block copolymer, different
morphologies from spherical to tubular and vesicle are formed that
can be reversibly expanded and contracted by addition and removal
of CO2 (Fig. 48).
Copolymerization of DEAEMA and S as the hydrophobic
block in PEO-b-(DEAEMA-r-S) led to the formation of CO2-
switchable self-assemblies with morphologies tuneable from
vesicle to spherical upon stimulus of CO2.114 However, PEO-b-
DEAEMA-b-S showed expansion only upon treating with CO2. In
another application of DEAEMA in the synthesis of CO2-
switchable polymers, multi-compartment micelles (MCMs)
with segregated corona were prepared, comprising a PEO (O)
shell and poly(2,2,3,4,4,4-hexafluorobutyl methacrylate) (F) and
PDEAEMA (E) core.117 The MCMs could be reversibly switched
‘‘on’’ and ‘‘off’’ by addition and removal of CO2, respectively.
After protonation of DEAEMA with bubbling CO2, the core was
segregated into two distinct phases while deprotonation of the
DEAEMA led to the reformation of uniform spherical micelles
(Fig. 49).
DEAEMA was used as a CO2-switchable monomer in the
synthesis of Pickering emulsifiers.193 The crosslinked polymer
particles were prepared via surfactant-free emulsion polymer-
ization (SFEP) of DEAEMA and sodium methacrylate (SMA) as a
stabilizer in the presence of N,N-methylenebis(acrylamide)
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Fig. 49 Molecular structure of the triblock copolymer O113F110E212 (a) and

schematic representation of the micellar morphology after sequentially
bubbling and removing CO2 (b); triblock copolymer (left); spherical micelle
with grey corona formed by the hydrophilic ‘‘O’’ block and purple core
formed by hydrophobic ‘‘E’’ and ‘‘F’’ blocks (centre); multi-compartment
micelle with a red core formed by the ‘‘F’’ block and phase-separated
corona, formed of blue charged ‘‘E’’ domains and grey ‘‘O’’ domains
(right).117 Reprinted from ref. 117 with permission from the RSC.

Diblock copolymers comprised of a PEG hydrophilic shell

Fig. 48 CO2-switchable triblock copolymer PEO-b-PS-b-PDEAEMA (OSA) and DEAEMA/FMA copolymer hydrophobic core have dual
and its CO2-driven controlled deformation.31 Reprinted from ref. 31 with
responsiveness to O2 and CO2.119 FMA is oxygen sensitive and
permission from ASC publications.
DEAEMA is a CO2-sensitive monomer. Bubbling CO2 protonates
the tertiary amine groups of DEAEMA and as a result interfacial
(MBA) crosslinker.193 The particles were zwitterionic in nature energy increases. Therefore, vesicles are transformed to micelles
because of the presence of oppositely charged DEAEMA and SMA. while bubbling O2 slightly increases the hydrophilicity of FMA
Bubbling CO2 led to the dissolution of particles while bubbling without any transformation from vesicles to micelles (Fig. 50).
N2 induced their precipitation. Switching on and off cycles were Dual CO2 and temperature responsive PDEAEMA60-b-PNIPAM40
performed at room temperature with relatively fast response to was synthesized via RAFT polymerization.28 PDEAEMA is hydro-
the triggers. In a similar work, Armes and co-workers prepared philic in its protonated form and hydrophobic in neutral form
Pickering emulsifiers via the emulsion polymerization of while PNIPAM is hydrophilic above its LCST and hydrophobic
DEAEMA and divinylbenzene (DVB) crosslinker.17 Polymeriza- below its LCST. In aqueous media, the diblock copolymer self-
tion was performed at 70 1C using monomethoxy-capped assembles into a vesicular morphology. By applying temperature
poly(ethylene glycol) methacrylate (PEGMA) as a reactive stabi- and/or CO2 the diblock copolymer self-assembles into spheres,
lizer. The resultant microgel particles were pH sensitive and vesicles, or unimers depending on the ratio of hydrophilic to
showed reversible increase and reduction in size upon addition hydrophobic blocks.28 This is the first example of a ‘‘schizophrenic’’
of acid (HCl) and base (KOH). However, an 80 nm reduction in diblock copolymer that shows a morphological transition from
the hydrodynamic diameter of particles was observed after micelles to unimers and from unimers to vesicles by applying CO2
10 cycles of switching on and off.17 Instead, when CO2 was
performed for the switching on process and N2 for the switching
off process, no significant reduction in the size of the particles
was detected even after 10 cycles. The main advantage of using
CO2 was that no salt accumulated in the system and therefore
did not have any negative impact on the particle morphology.
DEAEMA has also been used in the synthesis of magnetic
nanoparticles (MNPs) comprised of fluorescence-labelled
magnetic cores and a CO2-switchable shell.115 These nanoparticles
showed reversible expansion and contraction in response to CO2
and N2 triggers because of protonation and deprotonation of
DEAEMA. In another study, gold nanoparticles (AuNPs) were
functionalized by PDEAEMA to achieve CO2-switchability.118
Particles could be aggregated and redispersed by bubbling
Fig. 50 Synthesis routes of the CO2- and O2-sensitive diblock copolymer
CO2 and N2, respectively. The dispersion and recycling of the O2K-FN, and schematic representation of the CO2- and O2-driven self-
particles was adjustable by addition and removal of CO2 from a assembly and shape transformation behaviour of the vesicles.119 Reprinted
catalytic reaction solution. from ref. 119 with permission from ACS publications.

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Fig. 51 Schematic of the ‘‘schizophrenic’’ aggregation behaviour for the
diblock polymer PDEAEMA-b-PNIPAM controlled by CO2 and tempera-
ture.28 Reprinted from ref. 28 with permission from the RSC.
and temperature triggers (Fig. 51). Since the LCST of the PNIPMA
block is close to body temperature and PDEAEMA is also a CO2-
responsive block (biocompatible trigger), this block copolymer
could be interesting from a biomedical applications perspective.
The term ‘‘schizophrenic block copolymers’’ was introduced for the
first time by Armes’ group in 1998, and refers to ‘‘block copolymers
or surfactants which are capable of forming both micelles (A block
in core) and reverse micelles (B block in core) solely in aqueous
media’’.223,224
Dual-responsive triblock copolymer poly(oligo(ethylene glycol)
methyl ether methacrylate)-block-poly(N,N-diethylaminoethyl
methacrylate)-block-poly(2-(3-(2-aminophenyl)-ureido)ethyl metha-
crylate) (POEGMA-b-PDEAEMA-b-PAPUEMA) (ODA) was synthesized
via sequential RAFT polymerization.215 PAPUEMA is NO (nitric
acid) responsive. At pH 7.4 (the pKa of the OD diblock precursor
was determined to be B7.4), the triblock copolymer self-assembled
into micelles comprised of three layers: PDEAEMA outer cores,
PAPUEMA inner cores, and hydrophilic POEGMA coronas
(Fig. 52). Upon CO2 addition, PDEAEMA becomes protonated
and expands the micelle; subsequent addition of NO converts
the PAPUEMA block to more hydrophobic benzotriazole moi-
eties, which leads to a morphological transition from spherical
nanoparticles to nanorods.215
The block copolymer self-assembles into PDEAEMA/PAPUEMA-
core micelles at neutral pH without gas stimuli while bubbling CO2
increases the water solubility of PDEAEMA block and results in the
formation of PAPUEMA core micelles with swollen POEGMA/
PDEAEMA coronas. Further addition of NO transforms swollen
micelles to nanorods due to the formation of hydrophobic benzo-
triazole moieties. The original ODA micelles can directly from
nanorods with only NO stimulation.215
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Fig. 52 Schematic representation of the self-assembly of dual-responsive
triblock copolymer by the stimulation of CO2 and NO.215 Reprinted from
ref. 215 with permission from the RSC.
Gold nanoparticles (AuNPs) coated with a UV and CO2-responsive
polymer film (co-functionalised with diamine-terminated
ligands and azobenzene) exhibited responsiveness reversibly in
an orthogonal fashion.225 The composition of the coating could
be tuned to make nanoparticles capable of aggregating only
when both triggers (UV and CO2) are applied at the same time.
5.2. Self-assembly of polymers containing DMAEMA
PDMAEMA was used as a CO2-switchable block in the synthesis of
the CO2- and temperature-responsive triblock copolymer PNIPAM-
b-PCL-b-PDMAEMA.125 This block copolymer self-assembled in
water and formed vesicles, which could expand and contract upon
addition and removal of CO2 due to protonation and deprotona-
tion of the tertiary amine groups of PDMAEMA (Fig. 53).
The triblock copolymer p(MEO2MA180-co-DMAEMA38)-b-
PEO455-b-P(MEO2MA180-co-DMAEMA38) is soluble in cold water
but self-assembles to micelles upon heating due to an LCST of
B30 1C imparted by the thermo-responsive components
MEOMA and DMAEMA in the two ends blocks.14 However, after
treating with CO2, the block copolymer showed no LCST since
DMAEMA increases the LCST after protonation. The gel-to-sol
transition occurred at 37 1C. A reversible transition was observed
after purging argon (Ar) and removal of the CO2 (Fig. 54).
DMAEMA was employed in the synthesis of CO2-switchable
PDMAEMA-b-PS nanoparticles.126 These particles are sensitive
Fig. 53 Illustration for synthesis and self-assembly of the supramolecular
triblock copolymer PNIPAM-b-PCL-b-PDMAEMA, as well as their CO2-
temperature dual stimuli-responsive process.125 Reprinted from ref. 125
with permission from ACS publications.
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Fig. 54 Schematic illustration of CO2-induced gel-to-sol and reverse

sol-to-gel transition of hydrogels and the ABA triblock copolymer design
making use of CO2-switchable LCST.14 Reprinted from ref. 14 with permission
from ACS publications.

Fig. 56 The schematic self-assembly process of Py-PCL-b-P(NIPAM-co-

DMAEMA) and the CO2-temperature dual responses.217 Reprinted from
ref. 217 with permission from the RSC.

Fig. 55 (A) Reactions of side chains of PDMAEMA on nanoparticles’ surface

upon CO2 and N2 bubbling; (B) schematic illustration of dispersion of
nanoparticles in the presence/absence of CO2.126 Reprinted from ref. 126
with permission from Elsevier.

to CO2 and can be redispersed and coagulated by addition and

removal of CO2. The positively-charged tertiary amine groups of
the PDMAEMA shell provide enough stabilization for dispersing
spherical particles. Therefore, they have been considered as a
potential drug delivery system (Fig. 55).
Poly(3-caprolactone)-block-poly(N-isopropylacrylamide-co-N,N-
methylaminoethylethacrylate) terminated with a pyrene group
(Py-PCL-b-P(NIPAM-co-DMAEMA)) is an amphiphilic block copo-
lymer synthesized by combination of ring-opening polymeriza-
tion (ROP), dicyclohexylcarbodiimide (DCC) reaction, and RAFT
polymerization.217 DMAEMA is CO2 and temperature responsive
while NIPAM is only temperature responsive. Pyrene induces
fluorescence in the block copolymer. Both DMAEMA and NIPAM
are hydrophilic while PCL is hydrophobic. Therefore, the diblock
copolymer self-assembles in water into micelles with a P(NIPAM-
co-DMAEMA) shell and Py-PCL core (Fig. 56). Due to the LCST of
the shell (42 1C) the shell is transformed into a hydrophobic state
and the micelles aggregate. However, after bubbling CO2,
DMAEMA is converted to its bicarbonate salt and the shell block
becomes hydrophilic again. Removal of CO2 reverses the situation
and leads to the aggregation of the micelles.
PADS-b-PDMAEMA, synthesized by using RAFT polymeriza-
tion and click chemistry, self-assembled into vesicles because of
the amphiphilic nature of the copolymer.218 Bubbling CO2 for
20 min through the PADS-b-PDMAEMA solution expanded the size
of the vesicles from B500 nm to more than B1000 nm (Fig. 57).
Fig. 57 Self-assembly of PADS-b-PDMAEMA into vesicles and the rever-
sible vesicles-micelles/aggregates transformation under bubbling CO2/Ar
and heating/cooling (top) and the gas-switchable structural change of the
PADS and PDMAEMA segments (bottom).218 Reprinted from ref. 218 with
permission from the RSC.
In their neutral sates, PDMAEMA is hydrophilic and PADS is
hydrophobic while after protonation the tertiary amine groups of
PDMAEMA are protonated. At the same time, the hydrophilicity
of PADS also increases due to the protonation of its amidine
groups. The overall effect is expansion of the vesicles. The degree
of expansion depends on the time of CO2 bubbling. The removal
of CO2 by bubbling argon results in the deprotonation of tertiary
amines and amidines and vesicles contact. The expansion-
contraction cycle is reversible.218 Due to the LCST of the
PDMAEMA segment of the diblock copolymer, heating above
45 1C led to the transition of PDMAEMA from a hydrophilic to

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Fig. 58 CO2-switchability of the N-(2-aminoethyl)-5-(1,2-dithiolan-3-

yl)pentanamide (NADPA) SAM: (A) a photographic image of the water drop
profile on a NADPA modified surface before (left) and after (right) the
stimuli of dissolved CO2; (B) a schematic diagram of the stimuli-induced
transition of surface wettability; (C) changes of chemical structure of
amidine; (D) reversible switching of water contact angles. The error bars
represent the standard error derived from three measurements.226 Reprinted
from ref. 226 with permission from the RSC.

Fig. 59 Orthogonal connection of an end-decorated polysaccharide

hydrophobic state with the subsequent formation of micelles, (Dex-CD) and poly(L-valine) (BzI-PVal) to form supramolecular block
however, in the absence of CO2, micelles were not stable and glycopolypeptides and schematic illustration of their CO2-switchable
tended to aggregate.218 assembly and disassembly behaviour mimicking viral capsids.227 Reprinted
from ref. 227 with permission from ACS publications.
5.3. Other self-assemblies
N,N-Dimethylacetamide dimethyl acetal (DMADMA) was used
for the preparation of CO2-switchable surfaces containing
amidine groups with a self-assembled monolayer (SAM) on a
gold substrate.226 This surface is highly selective in the adsorp-
tion of hydrophobic/hydrophilic molecules (Fig. 58).
A ‘‘CO2-cleavable supramolecular block glycopolypeptide’’
prepared via the coupling of two biopolymers, dextran and
poly(L-valine),227 self-assembled into either vesicular or fibrous
morphologies depending on the length of each block (Fig. 59).
These vesicles and nanofibers are reversibly disassembled and
reassembled in water upon ‘‘breathing in’’ and ‘‘breathing out’’
CO2, respectively.
PFPA–DMA and PEGA–PFPA diblock copolymers were
synthesized via RAFT polymerization and then post-modified
to the corresponding histamine (HIS) dihydrochloride and Fig. 60 Gas-switchable amidine-containing triblock copolymer PEO-b-
66 PAD-b-PS (top) and representation of its CO2-driven controlled self-
L-arginine methyl ester (ARG) block copolymers. The DMA–HIS
assembly and shape transformation behaviour (bottom).207 Reprinted from
and PEGA–HIS diblock copolymers can further self-assemble in ref. 207 with permission from Wiley.
water to form CO2-switchable block copolymer aggregates. The
triblock copolymer PEO-b-PAD-b-PS self-assembles in water into
tubular morphologies and the resultant tubules are transformed able to drive enzymatic catalytic reactions by tuning the CO2
to vesicles after bubbling CO2 through the polymer solution.207 stimulation times. Therefore, it is predicted that these tuneable
Further bubbling of CO2 converts vesicles to spherical micelles vesicles will help scientists to mimic cytomembranes and analyze
(Fig. 60). cellular functions.30
CO2-switchable diblock copolymer PEO-b-PAD was synthesized A subtlety of selecting monomers for CO2-switchable materials
by ATRP, which can self-assemble into vesicular aggregates with a that is often not appreciated nor discussed in papers is the role of
size of B60 nm.29 Upon bubbling CO2 into the aqueous solution, concentration of the protonatable groups under the intended
the vesicles are expanded to 120 nm and their volume increases up conditions of CO2 switching. To achieve effective switching, the
to B800%. This process is reversible and by removing CO2, the initial pH of the system (under air for example), which is a factor of
vesicles contract back to their initial size and morphology (Fig. 61). the concentration of the protonatable groups, should be at least
The amount of expansion is tuneable by controlled addition of CO2. one pH unit above the pKaH of the switchable groups. When the
Further study showed that membrane permeability is tuneable by concentration of the protonatable groups is low, as is often the
regulating the time of bubbling CO2.30 These polymersomes were case when surfaces or complex structures (e.g. those resulting

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Fig. 61 Schematic representation of its self-assembly into vesicles and
their reversible gas-responsive ‘‘breathing’’ in aqueous media.29 Reprinted
from ref. 29 with permission from Elsevier.
from self-assembly) are involved, the initial pH will be too low
to yield effective switching with only CO2 addition/removal. If
this problem arises, the solution is to select a different mono-
mer with switchable groups having a lower pKaH.
6. Potential applications of
CO2-responsive polymers
As the potential for designing new types of polymeric materials
based on CO2-responsiveness is realized, ideas for creative, new
applications will follow. The following section reviews recent
applications, and illustrates where future opportunities for new
materials development reside. As is seen below, the scope of
applications already being explored is expansive, despite the
relatively recent development of CO2-switchable polymers.
6.1. CO2-switchable surfaces
The first CO2-switchable polymer brushes were reported by Zhao
and coworkers in 2013.116 Brushes were made of PDEAEMA
grafted onto a silicon or a gold surface by ATRP. PDEAEMA
becomes protonated and hydrophilic by passing CO2 through
the solution and deprotonated and hydrophobic by passing N2 at
room temperature. Therefore, these polymer brushes can be
reversibly switched on (extended form) and off (collapsed form)
upon bubbling CO2 and N2, respectively, through the solution.
The process of switching on and off via stimulation of CO2/N2 is
reversible and, unlike acids and bases triggers that cause con-
tamination of the solution by the accumulation of salt, can be
repeated many times.116 Also, it was shown that the conforma-
tional change in polymer brushes can be used in the reversible
capture and release of protein (Fig. 62).
Wang et al.226 synthesized NADP-amidine, NADPA, (NADP is
N-(2-aminoethyl)-5-(1,2-dithiolan-3-yl) pentanamide) and then
employed it for preparing a CO2-switchable surface with a self-
assembled monolayer (SAM) on gold substrates. The amidine
end group has higher basicity for CO2 binding and is capable of
fully reversible switching.226 On the other end, NADPA has a
disulphide group for its immobilization onto gold substrates by
strong covalent bonding. Therefore, this surface can be reversibly
protonated by CO2 in water, and thus have its hydrophilicity and
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Fig. 62 Schematic illustration of protein adsorption and release using
CO2-switchable polymer brushes. Collapsed polymer brushes (switched
off state) form a surface favourable for protein adsorption, while extended
polymer brushes (switched on) form a surface unfavourable for protein
adsorption, leading to the release of adsorbed proteins.116 Reprinted from
ref. 116 with permission from the RSC.
wettability reversibly switched. According to the sample model
containing oleylamine (hydrophobic) and citrate (hydrophilic)
capped Au NPs, this switchable surface is a highly selective
adsorbent in response to dissolved CO2 stimuli.226 In another work,
thiol-terminated PDEAEMA (SH-PDEAEMA) was introduced onto
AuNPs for preparation of CO2-switchable gold nanoparticles.118
Gas-responsive measurements show that the dispersing of the
PDEAEMA–AuNPs in aqueous media can be easily controlled by
adding or removing CO2 from solution. Purging CO2 switches on
PDEAEMA and converts it from hydrophobic to hydrophilic.
Thus, the PDEAEMA–AuNPs are dispersed in solution due to the
formation of hydrophilic ammonium bicarbonates groups in the
polymer chains. After removal of CO2 by passing N2 through
the solution, the PDEAEMA–AuNPs are coagulated due to the
transition of PDEAEMA chains from a hydrophilic to a hydrophobic
state. The switching on and off process is reversible without salt
accumulation in the solution.118 These functionalized AuNPs have
higher catalytic activity compared to non-functionalized Au NPs,
and are more easily recycled.
CO2-switchable PDEAEMA-modified magnetic nanoparticles
(MNPs) were prepared via ATRP by a ‘‘grafting from’’ method
from silica surfaces.115 The MNPs were composed of fluorescin
isothiocyanate-labelled magnetic silica core and CO2-switchable
PDEAEMA brushes. The MNPs were dye-labelled, which enables
the monitoring of the existence and movement of the particles
for bioapplications.115 The higher number of PDEAEMA brushes
on the surface of the MNPs enabled the adsorption of protein.115
Protein adsorption and release can be achieved by the stimulation
of CO2 and N2 due to CO2-switchability of PDEAEMA brushes.115
In another study on magnetic nanoparticles, CO2-switchable
MNPs were synthesized in a one-pot process employing diamino-
alkanes as the surfactant.228 One amine group binds to the metal
surface while the other one facing the solution acts as the
stimulus responder (Fig. 63). These MNPs exhibited excellent
CO2-switchability at room temperature. 1,8-Diaminooctane
showed the best performance in the synthesis of MNPs by
producing well-dispersed nanoparticles after the stimulation of
CO2 and also providing effective aggregation by the removal of
CO2 with purging N2.228
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Fig. 63 (a) Synthesis of CO2-responsive MNPs; (b) reversible redispersion–
aggregation of the MNPs by alternate purging with CO2 and N2.228
Reprinted from ref. 228 with permission from Wiley.
Magnetic nanoparticles (MNPs) were homogeneously coated
on a silica surface with the thickness of 18  2 nm.229 3-(Tri-
methoxysilyl)propyl methacrylate (MPS) was then used to create
a polymer shell with carbon–carbon double bonds connected to
the MNPs. Subsequently, PDMAEMA was polymerized in the
presence of DVB cross-linker by distillation–precipitation poly-
merization (Fig. 64). The size of the MNPs was adjustable by
alternate CO2/N2 treatment due to contraction/expansion tran-
sitions because of the CO2 responsiveness of the PDMAEMA
shell.229 Importantly, in vitro drug release experiments with
doxorubicin (DOX) confirmed a time-controllable dosage
(Fig. 65). With the stimulation of CO2, the PDMAEMA shell
expanded and resulted in a significant increase in the drug
release rate; removal of CO2 lowered the drug release rate.
Furthermore, the in vitro cytotoxicity experiment demonstrated
that these MNPs had good biocompatibility.
By incorporating the amino-terminated self-assembled mono-
layers (SAMs) onto silicon substrates and exposing CO2, surface-
bound carbamate structures were produced.230 Switching from
Fig. 64 Schematic illustration of the synthesis of PDMAEMA modified
core–shell–corona MNPs.229 Reprinted from ref. 229 with permission
from the RSC.
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Fig. 65 (A) Schematic representation of CO2-switchable dosage drug release
by MNPs. (B) The DOX release profiles from Fe3O4@SiO2–PDMAEMA
nanoparticles in response to alternate CO2/N2 stimulation.229 Reprinted
from ref. 229 with permission from the RSC.
neutral to charged character via bubbling CO2 led to a change in
surface polarity and electrostatic properties. The entire process
was both tuneable and reversible.230
6.2. CO2-switchable latexes
Conventional methods for settling surfactant-stabilized latex
dispersions include addition of a salt, an acid for a latex
stabilized by anionic surfactants, or a base for a latex stabilized
by cationic surfactants.231,232 Addition of chemicals such as
acids or bases causes salt accumulation in the system. To
overcome this problem, a CO2-switchable latex was reported
by our group.7 Long-chain alkyl amidine compounds were used
as CO2-switchable surfactants in the emulsion polymerization
of styrene. After the polymerization, removal of CO2 by bubbling
of Ar at 65 1C triggered the coagulation of the PS latex. Also, we
prepared CO2-switchable PS and PMMA latexes employing
amidine-based switchable surfactants.8 In each case the latexes
could be coagulated by removal of the CO2. It was found that
initiator and surfactant selection is crucial in preparing CO2-
switchable latexes. For example, VA-044 causes the permanent
stability of latexes even in the absence of CO2.8 Shortly after, our
group prepared for the first time coagulatable and redispersible
CO2-switchable PS latexes.9 When both initiator and surfactant
are CO2-switchable, redispersion of latexes can be performed
more effective. The aggregation and redispersion of latexes were
possible for several cycles without accumulation of any back-
ground salt.9
Aryl amidines and tertiary amines are less basic than alkyl
amidines; as a result they are switched off much more rapidly.10
Long chain tertiary amine switchable surfactants are commer-
cially available and have lower cost compared with aryl amidine
based surfactants. PMMA latexes made using tertiary amine
and aryl amidine based surfactants were destabilized much
more easily by bubbling Ar to remove the CO2 and had lower
zeta potentials than those prepared with alkyl amine based
surfactants.10 CO2-switchable PS latexes were made under CO2
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Table 5 Decomposition kinetics of VA-061 and VA-044 in different

atmospheres and solvents.a 11 Reproduced from ref. 11 with permission
from ACS publications
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Ed, 105
Initiator Solvent Atmosphere J mol1 Ad, 1013 s1 T10 h half-life, 1C
VA-044 D2O Argon 1.07 1.22 43
VA-061 CD3OD Argon 1.15 1.30 60
VA-061 D2O CO2 1.07 1.11 42
VA-044b H2O c
1.08 1.21 44
VA-061b CH3OH c 1.14 1.29 61
a
Ed: activation energy; Ad: pre-exponential factor; T10 h half-life: 10 h half-
life decomposition temperature. b The data from the web site of Wako
Pure Chemical Industries, Ltd. c Presumably air.

atmosphere in surfactant-free emulsion polymerization using

VA-061 as both initiator and stabilizer.11 According to the
calculations of the decomposition rate parameters, the 10 h
half-life temperature (T10 h half-life) of VA-061 under a CO2 atmo-
sphere was found to be similar to the T10 h half-life of VA-044
Fig. 66 Photographs and TEM and SEM micrographs of the original latex
under an Ar atmosphere (Table 5).
(left), after destabilization in the presence of poly(DEAEMA) (middle) and
The polymerization was performed at 70 1C, which gave redispersed after 10 min of sonication under CO2 atmosphere (right).12
good polymerization rates but may have resulted in the amidine Reprinted from ref. 12 with permission from ACS publications.
groups on the initiator being only partially protonated due to the
lower solubility of CO2 at this high temperature. Therefore, the
achievable solid content was low (B7%). Because imidazole
groups created from the decomposition of VA-061 are bonded
covalently to the surface of the latex particles, unlike switchable
surfactant, they cannot detach from the latex particles during
destabilization. Thus, upon bubbling CO2 they can be proto-
nated again and re-stabilize latex particles. To increase solid
content, polymerization was repeated at 65 1C and 0.54 mol%
DEAEMA was used as a CO2-switchable comonomer to prepare a
CO2-switchable and monodispersed PS latex.12 It was found that
adding a few mole percent MMA can increase the conversion
considerably because MMA is more hydrophilic than styrene and
produces more hydrophobic oligomers in the aqueous phase,
thereby promoting particle nucleation. Hydrophilic poly-
(DEAEMA+HCO3) formed during the reaction acts as a CO2-
switchable-flocculant and causes easy coagulation and redisper-
sion of the latex.12 After destabilization and drying, the latex
could be re-dispersed by CO2 bubbling and sonication (Fig. 66).
Using DEAEMA in the protonated form as a comonomer with Fig. 67 Synthesis of amidine-containing styrene comonomer and its
VA-044 as the initiator in the SFEP of styrene resulted in an easily emulsion copolymerization with styrene, as well as a schematic illustration
redispersible latex that could be dried and then readily redispersed of reversible coagulation and redispersion of PS latex triggered by CO2 and
a small amount of NaOH.192 Reprinted from ref. 192 with permission from
by mixing with water and applying only a short sonication time.128
ACS publications.
An amidine-containing styrene derivative was synthesized
and then employed as a CO2-switchable comonomer in the
surfactant-free emulsion polymerization of styrene.192 Since (N-amidino)dodecyl acrylamide was synthesized as a CO2-switchable
2,20 -azobis(2-methylpropionamidine)dihydrochloride (V-50), which surfactant and then employed in the emulsion polymerization of
is the HCl salt form of the initiator, was used as a positively charged styrene. However about 20% hydrolysis of the amidine was observed
initiator, destabilization of the latex was only possible by addition in the surfactant during the reaction.1 The PS latexes were stable
of a small amount of strong base (NaOH). However, the coagulated against electrolytes and could be coagulated and redispersed
latex was redispersible after CO2 bubbling followed by sonica- several times.
tion.192 The coagulated, filtered and dried latex powder was also To overcome the hydrolysis problem and simplify the synth-
redispersible using CO2 and ultrasound (Fig. 67). esis steps, DMAEMA was employed in the preparation of
In another study, CO2-switchable PS latexes were prepared PDMAEMA-b-PMMA via RAFT polymerization.101 This diblock
using VA-061 as a CO2-switchable initiator.1 In this process, copolymer was used as a polymeric surfactant in the emulsion

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Fig. 68 Illustration of reversibly coagulatable and redispersible PMMA
latex particles prepared by PDMAEMA-b-PMMA.101 Reprinted from
ref. 101 with permission from Wiley.
polymerization of MMA. To keep the surfactant protonated
during the reaction, protonation was done by HCl. The resultant
latex could be coagulated by addition of a small amount of base.
After washing with DI water, the latex could be redispersed and
coagulated many times by addition and removal of CO2 (Fig. 68).
It was found that the latex would be stable if the weight fraction
of MMA (FMMA) in the surfactant was lower than 58%.77 Particle
size decreases when FMMA increases.
An advantage of using polymeric surfactants is the prevention
of surfactant migration in film-forming applications. When
latexes are employed as film-forming polymers, physically
adsorbed surfactants on the surface of the particles migrate
toward the interfaces and lead to phase separation that reduces
gloss and adhesion.76 Also, they can be entrapped in pockets and
increase percolation by water or increase water sensitivity of the
film. These are major drawbacks for paint and coating applica-
tions.75,76 Surfactants that are covalently linked to the particles
cannot desorb and migrate during film formation.
CO2-switchable PMMA and PS latexes were prepared using
commercially available N,N-dimethyldodecylamine (DDA), a
CO2-switchable surfactant, via miniemulsion polymerization.106
The PMMA latexes could be aggregated by bubbling argon (Ar) at
60 1C and redispersed by bubbling CO2 at room temperature.
DDA is protonated by bubbling CO2 in the solution and converted
to DDAH+HCO3 but some deprotonation occurs after sonication
or during the reaction at elevated temperatures.106 At 80 1C, 40%
of DDAH+HCO3 switched back to DDA after 2 h. PS latexes
were not destabilized only by bubbling Ar. The reason could be
attributed to the lower density of PS latex (1.05 g cm3)
compared to PM latex (1.18 g cm3).106 However, increasing
the pH to 9 resulted in the aggregation of PS latexes because of
the decrease in the hydration effect of the tertiary amine. Since
the PS nanoparticles contained some hexadecane with a density
of 0.77 g cm3, the final density of the PS latex was lower than
1 and it flocculated on the surface of the water.106 In a dispersion
of nanoparticles composed of a DDA hydrophobic core and
polyvinylformal (PVF) shell, bubbling CO2 converted the core
from hydrophobic to hydrophilic, which was the first report of
preparing water-core polymer capsules from O/W emulsions
(Fig. 69).
N-Methacryloyl-11-aminoundecanoic acid was employed as a
CO2-switchable comonomer and stabilizer in the preparation of
4418 | Chem. Soc. Rev., 2016, 45, 4391--4436
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Fig. 69 SEM and TEM images of PVF colloids: (a & b) with DDA as the
core; (c) and (d) with water core. PVF capsules were prepared by using PVF
and DDA (4 : 1 by weight).106 Reprinted from ref. 106 with permission from
the RSC.
PS latexes via surfactant-free miniemulsion polymerization.233
Latex particles were coagulated by bubbling CO2 due to protonation
of carboxyl groups and redispersed by ultrasonication due to
removal of CO2 from the solution. According to DLS and zeta
potential measurements, redispersion and coagulation processes
were repeatable. Surfactant-free miniemulsion polymerization has
also been used for the preparation of CO2-switchable PDMAEMA-b-
PS nanoparticles.126 The resultant particles had a core-shell
structure with a mean diameter of 120 nm.
Using a different approach, a CO2-switchable latex can be
produced by using non-switchable components including initiator,
monomer, and surfactant.54 In this method, the stability of the
latex is controlled by adding a ‘‘switchable water’’ ionogen to
the aqueous phase. In switchable water, the ionic strength of
the aqueous solution can be switched between low and high
values by addition and removal of CO2.54 This change occurs
because an amine or polyamine called an ionogen is reversibly
converted from a neutral to a bicarbonate salt by the action of
CO2. For example, sodium dodecylsulfate (SDS), in the absence
of an ionogen, is not CO2-switchable but the aqueous solution
of SDS and N,N-dimethylethanolamine (DMEA, an ionogen) has
CO2-switchable air/water surface tension (Fig. 70). A PS latex
stabilized by SDS can be aggregated by bubbling CO2 and
redispersed by bubbling Ar (to remove CO2).54 Since the latex
was prepared with potassium persulfate (KPS) initiator, the
aqueous solution was acidic. Therefore, the initial pH was lower
than the pKa of carbonic acid and prevented neutralization of
the amine group by removal of CO2. Fig. 71 shows the results as
the latex was neutralized by NaOH and then treated with DMEA
ionogen, after which the latex was CO2-responsive.
CO2 has also been used for tuning microemulsion aggrega-
tion.234,235 Reactive ionic liquids were employed in the preparation
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Fig. 70 Air/water surface tension as a function of the concentration of
aqueous solutions of SDS under air or CO2 and in the presence or absence
of DMEA (33.0% v/v) under air or CO2 at (25  0.5) 1C.54 Reprinted from
ref. 54 with permission from Wiley.
Fig. 71 Reversible aggregation/redispersion of a PS latex prepared by using
styrene (15 mL), SDS (0.50 g), KPS (0.10 g) and water (50 mL). A solution of
NaOH, DMEA (5 mL) was added to the sample and then CO2 was purged
with the flow rate of 90 mL min1 at room temperature for 10 min. Then,
argon was purged with the flow rate of 90 mL min1 at room temperature
for 10 min.54 Reprinted from ref. 54 with permission from Wiley.
of a CO2-switchable microemulsion.235 In a microemulsion
system containing cyclohexane, surfactant (1-hexadecyl-3-methyl-
imidazolium chloride (C16mimCl) and decanol, with mole ratio
of 1 : 2), and ionic liquid (1-butyl-3-methylimidazolium triazolide
([bmim][tria123])), the nanodomains can be reversibly tuned by
addition and removal of CO2.235
Silica particles prepared in surfactant-free emulsions using
only CO2-switchable chemical functional groups can stabilize
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Fig. 72 Schematic representation of coagulation and redispersion of latex
particles with Tg higher than ambient temperature and lower than ambient
temperature.13 Reprinted from ref. 13 with permission from Wiley.
oil-in-water emulsions, while particles containing both CO2-
switchable and hydrophobic functional groups on their surface
are able to stabilize water-in oil emulsions.236 Emulsions are
broken when CO2 is introduced due to the alteration of the
wettability of the stabilizing particles which leads to phase
separation of the emulsions. The stability is re-established by
bubbling air and CO2 removal. CO2 creates a positive charge on
the surface of the responsive particles, increasing hydrophilicity
and as a result the particles destabilize the emulsion.236
Acrylic latexes with low Tg were prepared in surfactant-free
emulsion polymerization (SFEP) of MMA and BA with a small
amount of DEAEMA as a CO2-switchable comonomer.13 The Tg
of the copolymer was adjusted by the combination of MMA and
BA. If the Tg is higher than room temperature, the latex is CO2-
redispersible while if the Tg is lower than ambient temperature,
after coagulation, latex particles begin to fuse and are not easily
CO2-redispersible (Fig. 72). However, if the same low-Tg latexes
are coagulated at temperatures lower than their Tg, they can be
redispersed by bubbling CO2 and using ultrasound.
In most of the publications reviewed in this section, redispersion
of the latexes was achieved using sonication, which is an energy-
intensive process and not viable industrially. Further development
of CO2-responsive latexes (especially low Tg latexes) that can be
coagulated and redispersed without applying sonication, and only
requiring gentle mixing and bubbling CO2 would be useful. To
overcome this barrier, the main focus should be on the prevention of
the interdiffusion of polymer chains between adjacent latex particles
after coagulation. This would also ensure the CO2-responsive
functional groups on the surface of the particles are not buried
between diffused particles and as a result redispersion of those
particles would be much easier.
6.3. CO2-switchable gels
Polymeric systems that can undergo a deliberately triggered
change in viscosity from non-viscous liquid to gels or high viscosity
solutions have been intensively studied in recent years. Adopting
CO2-switchable technology to these materials has progressed rapidly
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as the advantages of CO2-switching has become more widely
recognized. In particular the ability to synthesize systems
capable of undergoing multiple reversible gelation cycles with-
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out degradation in performance is valued (since there is no salt
accumulation with each cycle, as occurs with pH switching using
liquid acids/bases). Triblock copolymer hydrogels comprised of
P(MEO2MA180-co-DMAEMA38)-b-PEO455-b-P(MEO2MA180-co-DMAEMA38)
which were both temperature and CO2-switchable due to the
existence of DMAEMA, have also been reported.14 Both blocks
were water-soluble in cold water while upon heating to B30 1C
the two end-blocks containing DMAEMA became hydrophobic
because of the LCST of DMAEMA, thereby forming micelles.
When CO2 was bubbled in the triblock copolymer solution, the
LCST of the copolymer increased to 60 1C due to the protona-
tion of DMAEMA.14 The dissociation of micelles to free polymer
chains (sol formation) upon treating with CO2 was reversible,
Bubbling Ar (removing CO2) led to the formation of micelles
(gel formation). Using MAA instead of DMAEMA resulted in the
formation of P(MEO2MA160-co-MAA36)-b-PEO455-b-P(MEO2MA160-
co-MAA36) which displayed a reversible sol-to-gel transition upon
bubbling CO2 and Ar, respectively (Fig. 73).14
Another dual temperature and CO2-responsive copolymer
composed of poly(NIPAM-co-DMAPM) micro-nanogel particles
was synthesized, which could capture and release CO2 by cooling
and heating, respectively.15 At temperatures lower than the phase-
transition temperature (PTT), NIPAM is water-soluble and as a
result the gel particles are swollen. Therefore, they can form ion
pairs with absorbed bicarbonate ions. At temperatures higher than
PTT, the gel particles shrink and thus the number of amine groups
in contact with water decreases. As a result, CO2 is desorbed almost
completely.15 Also dual responsive hydrogel films composed of
temperature and CO2-switchable moieties have been synthesized
with significant CO2 absorption capacity after addition of a small
amount of water.237 These films had faster and greater capture and
release of CO2 compared to monolithic gel films.
CO2 was used as a gellant in the synthesis of polyallylamine
(PAA) based hydrogels.16 PAA was crosslinked with CO2 using
1,8-diazabicyclo[5,4,0]-undec-7-ene (DBU) as cross linker. The
obtained hydrogels were capable of reversible capture and release
of CO2 with high absorption capacity (4 times more than that of
Fig. 73 Photographs showing the reversible gel-to-sol transition of
P(MEO2MA180-co-DMAEMA38)-b-PEO455-b-P(MEO2MA180-co-DMAEMA38)
upon alternating bubbling with CO2 and Ar at 37 1C (top) and reversible
sol-to-gel transition of P(MEO2MA160-co-MAA36)-b-PEO455-b-P(MEO2MA160-
co-MAA36) upon alternating bubbling with CO2 and Ar at 35 1C (bottom).14
Reprinted from ref. 14 with permission from ACS publications.
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Fig. 74 Reversible CO2 absorbing hydrogel.16 Reprinted from ref. 16 with
permission from Wiley.
PAA aqueous solution and 2.8 times more than that of the mono-
ethanolamine).16 These hydrogels can completely desorb CO2 under
N2 atmosphere at higher temperatures (Fig. 74).
Polysiloxanes are among the most studied polymers since the low
energy of interaction among their chains creates two interesting
properties: relatively low viscosity and high malleability.238
These properties can also be disadvantageous because without
crosslinking, polysiloxanes cannot be used for making fibers
and immobilized films and in most cases crosslinking is not
reversible.238 To address this problem, a simple method has been
developed to convert weakly interacting chains of polysiloxanes in an
uncharged state with substituent amine groups to strongly
interacting chains via electrostatic attractions between negative
and positive centres.238 This electrostatic attraction leads to
crosslinking that changes the thermal, rheological, and adhesive
properties of polysiloxanes. Bubbling CO2 results in an increase
in viscosity and adhesiveness of several orders of magnitude.238
The process can be reversed by heating the polymer and bubbling
N2 through it. The whole process is reversible and repeatable
without detectable degradation (Fig. 75).
It has been reported that polyallylamine (PAA) reacts with
CO2 in water to form polyallylammonium polyallylcarbamates,
which act as crosslinkers and lead to the aggregation of the PAA
chains in the form of a turbid dispersion.239 Further reaction with
CO2 reduces the crosslinking density, and results in dissociation of
the PAA chains into smaller aggregates, observed as a transparent
dispersion. However, removal of CO2 from the transparent
dispersion enhances the crosslinking density and produces the
larger aggregates again (Fig. 76).
A series of poly(DMAEMA-co-acrylamide) copolymers was
synthesized with varying ratios of AM and DMAEMA, which
interestingly exhibited CO2-switchable viscosity.124 It was found
Fig. 75 Structures of polysiloxane samples and a general scheme for their
reactions with CO2.238 Reproduced from ref. 238 with permission from
ACS publications.
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Fig. 78 Synthesis route of P(DEA-co-FS) microgel and schematic repre-

sentation of its CO2 and O2-responsive behaviour.241 Reprinted from
ref. 241 with permission from ACS publications.

Fig. 76 Reversible PAA chain association/dissociation in water via a CO2

switchable crosslinking/decrosslinking.239 Reproduced from ref. 239 with
permission from the RSC.

that the tertiary amine groups of the copolymer experience a

reversible switch between hydrophobic and hydrophilic state
upon CO2 addition and removal, which results in different
rheological behaviors.124
The transition of liquid-like materials into a solid-like glassy
state due to a rapid increase in density or decrease in temperature is
known as a jamming transition.240 The concept of jamming has
been introduced into a CO2-responsive microgel suspension by
protonation of cross-linked DMAEMA microgels.240 The particle size
of the synthesized microgels increased significantly by bubbling CO2
and the rheological properties of the PDMAEMA suspension were
CO2-responsive. When CO2 was bubbled into the microgel, at a
certain concentration of the microgel and at a specific pH, the
Fig. 79 Changes in the particle size of P(DEA-co-FS) microgels (run 3)
microgel suspension rapidly and reversibly transformed to a solid-
during two cycles of CO2, O2, and N2 treatments.241 Reprinted from
like glassy state due to the jamming of particles. The liquid-like form ref. 241 with permission from ACS publications.
of the suspension was recoverable upon the removal of CO2.240
Armes and coworkers prepared CO2-switchable microgel
particles via SFEP of DEAEMA using monomethoxy-capped Pyridine-functionalized PNIPAM-based microgels were synthe-
poly(ethylene glycol) methacrylate (PEGMA) as the steric stabi- sized and subsequently placed between two thin Au layers to form
lizer and APS initiator in the presence of DVB crosslinker.17 a structured photonic device (Fig. 80).242 The resultant etalons were
Microgel particles expanded and contracted by addition and dual temperature and CO2-responsive due to the existence of NIPAM
removal of CO2 without significant change in the size of the and pyridine, respectively. The CO2-switchability investigation
expanded particles up to 10 cycles due to the lack of back- showed an optical response of the device to CO2. The protonation
ground salt (Fig. 77). of pyridine groups caused the expansion of microgel, which was
Emulsion copolymerization of 2,3,4,5,6-pentafluorostyrene similar to a ‘‘microgel breathing process’’.
(FS) as an O2-switchable monomer along with DEAEMA as a CO2-switchable PDMAEMA-based hydrogels have been used
CO2-switchable monomer in the presence of N,N 0 -methylenebis- as antidote delivery vehicles.243 The hydrogels were crosslinked
(acrylamide) (BisAM) crosslinker and V-50 initiator led to the by trimethylolpropane trimethacrylate. Expansion of these
formation of dual O2 and CO2 responsive microgel particles
(Fig. 78).241 The particles experienced significant volume change
with O2 and/or CO2 stimulation (Fig. 79).

Fig. 77 Expansion and contraction of PDEAEMA microgel particles cross-

linked with DVB and stabilized by PEGMA macromonomer.17 Reprinted Fig. 80 (a) Microgel synthesis scheme, and (b) etalon fabrication process.242
from ref. 17 with permission from ACS publications. Reprinted from ref. 242 with permission from the RSC.

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hydrogels was controllable by the stimulation of CO2. Therefore

controlled swelling of these hydrogels led to the controlled release
of naloxone.243 A significant control over naloxone release was
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attained in terms of the concentration of the biomarker.

A CO2-switchable sol to gel transition system composed of a
triblock copolymer was synthesized by ATRP in aqueous nano-
clays dispersions.205 The middle block was poly(ethylene oxide)
(PEO) and the two end blocks were PDMAEMA. The aqueous
mixture is CO2-responsive and changes from a low viscous sol
to a self-healable gel in the presence of CO2 due to the
protonation of PDMAEMA blocks, which makes bridge with the
negative charges of nanoclays and forms a physical network. Upon
removal of CO2, the gel is transformed to sol due to deprotonation
of PDMAEMA. The whole process is fully reversible. The hydrogel
has remarkable self-healing ability and thus it is believed that this
system can be employed for a wide range of applications including
Fig. 81 Different geometries formed by block copolymers in selective
intelligent delivery systems, biomaterial fields, and enhanced oil
solvent conditions.247 Reprinted from ref. 247 with permission from
recovery (EOR). Elsevier.
Quickly-responding switchable microgels of DEAEMA stabilized
with PEGMA were obtained by emulsion polymerization.244 These
PDEAEMA-PEGMA microgels collapse within just 5 seconds of materials such as genes, anticancer drugs, proteins, and diagnostic
bubbling CO2 into the solution; the fast response was attributed probes.258 Recently stimuli-responsive vesicles have attracted
to the high density of tertiary amine groups in DEAEMA and the attention as novel delivery systems. The main advantage of these
relatively weak crosslinking degree of DEAEMA. types of vesicles is that the release of the encapsulated contents
is adjustable to the stimulus. Also, because of the stimuli-
6.4. CO2-switchable vesicles (polymersomes) responsive release, therapeutic efficacy is significantly enhanced
Block copolymers can self-assemble into different morphologies and side effects are minimized.258 In many applications release of
such as vesicles, spheres, and tubules (depends on the blocks the substances encapsulated in the vesicles should be controllable,
lengths and Flory–Huggins interaction parameters) when they and stimuli-responsive vesicles can address this problem.259 CO2 as
are dissolved in a selective solvent (a solvent that is good for one a biocompatible stimulus can be employed to induce polymer
block and is a precipitant for the other block).245,246 Several vesicular morphological transitions.28 For example, a dual tem-
aspects of the morphological characteristics in vesicles such as perature- and CO2-switchable PDEAEMA-b-PPNIPAM was synthe-
wall thickness, size, surface topology, and deformation have sized via RAFT polymerization and the resultant diblock copolymer
been discussed in the review by Mai and Eisenberg.245 The self-assembled into dual-responsive vesicles.28 Bubbling CO2 in the
packing parameter ( p) is defined as p = v/(a0d) where v is the aqueous solution protonated the DEAEMA block, and as a result,
volume and d is the length of the soluble block in the selective the diblock copolymer was converted to free polymer chains. Then,
solvent, and a0 is the interface area between the solvent-phobic heating polymer chains to temperatures higher than the LCST of
and solvent-philic blocks. As shown in Fig. 81, polymer the copolymer led to the precipitation of the NIPAM block and
membrane, polymer cylindrical micelles, and polymer spherical formation of spherical particles with a NIPAM core and a DEAEMA
micelles are formed when 1/2 o p r 1, 1/3 o p r 1/2, and shell (Fig. 82).
p r 1/3, respectively.247 The CO2-switchable amphiphilic diblock copolymer poly-
Block copolymers have been used extensively in emulsion and (ethylene oxide)-b-poly((N-amidino)dodecyl acrylamide), prepared
dispersion polymerization.248,249 They can also be employed as via ATRP, formed vesicles in aqueous solution.29 Upon bubbling
vehicles for controlled drug delivery. Leroux et al. have reviewed
the preparation, characterization and applications of block
copolymer micelles in drug delivery systems.250 Eisenberg and
coworkers251,252 reported for the first time the vesicle morphology
of block copolymers by observing TEM images of the self-assembly
of PS-b-PAA block copolymers in aqueous solutions. Vesicles
or polymersomes have been widely studied in biomedical
research and specifically in drug delivery.253–257 Liposomes
are self-assembled from low molecular weight lipids while poly-
mersomes are generally prepared from amphiphilic diblock
copolymers.258 Polymersomes have many unique advantages Fig. 82 Schematic illustrations of the CO2 and temperature driven self-
including high stability, tuneable membrane properties, and assembly process of PDEAEMA-b-PNIPAM.28 Reprinted from ref. 28 with
capability of carrying hydrophobic as well as hydrophilic permission from the RSC.

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Fig. 85 Schematic representation of CO2-induced vesicle to spherical

micelle transition (top) for random copolymer Pr as well as the vesicles
formed by the triblock counterpart Pb (bottom).114 Reprinted from ref. 114
Fig. 83 (a) TEM image and (b) DLS data for self-assembled PEO-b-PAD with permission from the RSC.
aggregates in the absence of CO2; (c) TEM image and (d) DLS data for self-
assembled PEO-b-PAD aggregates in the presence of CO2. Insets are
magnified images.29 Reprinted from ref. 29 with permission from Wiley. block copolymer self-assembled into vesicles in aqueous solution.113
After treating with CO2, these vesicles undergo morphological
transitions from expansion to complete dissociation depending
CO2 some of the tertiary amines of the second block were on the time of stimulation. However, crosslinked PEO-b-
protonated, which resulted in the expansion of the vesicles P(DEAEMA-co-CMA) could not be dissociated to free polymer
(Fig. 83). The amount of expansion depended on the time and chains and only showed reversible expansion and contraction
amount of CO2 bubbling. The expanded vesicles could be upon bubbling CO2 and Ar. PEO-b-PADAm-b-PS (EAS) prepared
reversibly contracted by bubbling Ar. Since the size of these via sequential ATRP self-assembled into tubules in water.207
polymersomes was tuneable, later it was shown that they can be These aggregates morphologically changed to vesicles upon
used as miniature separators (Fig. 84). Then, it was shown that introduction of CO2 and then to spherical particles upon further
theses vesicles are able to tune various enzymatic catalytic treatment with CO2 (Fig. 86).
reactions by regulating CO2 stimulation time.30 CO2-switchable triblock copolymers comprised of a CO2-
Block copolymers of PEO45-b-(DEAEMA90-r-St66) (polymer Pr) switchable interior core PDEAEMA (A), middle hydrophobic
and PEO45-b-DEAEMA93-b-St66 (polymer Pb) both self-assemble
into vesicles in aqueous solution.114 After bubbling CO2, the
vesicles of polymer Pr transform into spherical micelles, whereas
that of the polymer Pb showed an expansion (Fig. 85). It was
predicted that the limited hydration (degree of protonation was
35%) of the CO2-switchable tertiary amines caused by the steric
hindrance effect of adjacent groups (styrene groups) in polymer
Pr is responsible for the morphological transformation.
When DEAEMA was used as a hydrophobic block in the
synthesis of a CO2-switchable PDMA-b-PDEAEMA, the amphiphilic

Fig. 84 Illustration of the polymersomes acting as size-selective nano- Fig. 86 Representation of the CO2-driven self-assembly process and
separators modulated by CO2 levels.30 Reprinted from ref. 30 with permis- successive shape evolution of EAS aggregates.207 Reprinted from ref. 207
sion from Wiley. with permission from Wiley.

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Fig. 87 CO2-driven O113S211A59 vesicular shape transformation as mon-

itored by TEM: (a) no stimulus and (b) gas-triggered 30 min (scale bars:
500 nm).31 Reprinted from ref. 31 with permission from ACS publications.

PS (S), and hydrophilic outer layer of PEO (O) self-assembled in

nanostructures containing vesicles, worm-like micelles and
spherical micelles.31 Bubbling CO2 leads to the protonation of
the PDEAEMA block, and because the A chains have been
confined by the S chains, only the former is able to be hydrated.
Therefore, repulsive forces of charged PDEAEMA chains and
simultaneous restricted hydration of the core chains act as a
driving force for reassembling of the nanostructures.31 In the
case of vesicles, they are transformed from typical vesicles to
dozens of smaller irregular vacuoles (Fig. 87).
Li and coworkers studied the effect of compressed CO2 on the
aggregation micellization behaviour of zwitterionic–anionic (dodecyl
sulfonatebetaine)–(sodium bis(2-ethylhexyl) sulfosuccinate), DSB–
AOT, mixed surfactants in aqueous media via direct observations Fig. 88 (a) Controlled release of DOX from PADS-b-PDMAEMA vesicles
such as steady-state fluorescence, turbidity, entrapment quantity or micelles/aggregates at different conditions and (b) controlled release of
DOX from PADS-b-PDMAEMA vesicles without stimuli and with alternating
of vesicles, and fluorescence quantum yield.260 Interestingly, all
CO2/Ar stimuli.218 Reprinted from ref. 218 with permission from the RSC.
measurements confirmed that CO2 induced micelle to vesicle
transitions in this zwitterionic–anionic surfactant system. This
CO2-induced transition was reversible and the degree of transition
could be readily controlled by the CO2 operating pressure.260
PADS-b-PDMAEMA synthesized with RAFT polymerization
and click chemistry self-assembled into vesicles due to the
amphiphilic nature of the diblock copolymer.218 DOX, a typical
hydrophobic anticancer drug, was located in the hydrophobic PADS
membranes to investigate the controlled release of the drug from
the vesicles (Fig. 88). Expansion–contraction of the vesicles with
alternating CO2/Ar bubbling led to changes in the rate of release of
the drug compared to the release curve of DOX at 25 1C.
It was shown that vesicles are immediately formed in the
aqueous solutions of N-decylimidazole at pH B 5.8 to 6.2.261
The pH can be adjusted by bubbling CO2 and the size of the
Fig. 89 The structure of polymersomes after CO2 treatment formed by
vesicles does not change in the repeated cycles. A CO2-switchable
self-assembly in water and the necklace-like aggregates formed by
segmented diblock copolymer comprised of one random block removing CO2.123 Reprinted from ref. 123 with permission from the RSC.
was synthesized by RAFT polymerization using DEAEMA as a
CO2-switchable monomer.123 The hydrophilic block was PEO
while the random block was composed of 90 units of 4VP and ionic liquids, oxyfuel combustion, oxyfuel circulating fluidized
30 units of DEAEMA (PEO113-b-p(4VP90-r-DEAEMA30)). This block bed combustion (CFBC), chemical-looping combustion, calcium
copolymer self-assembled into vesicles and then giant worm-like looping, low temperature adsorbents, and direct air capture
micelles in aqueous solution. However, after bubbling CO2 into technology. D’Alessandro and coworkers263 have reviewed CO2
the solution the diblock copolymer transformed into polymer- capture by metal organic frameworks, chemical and physical
somes (Fig. 89). adsorption, solvent absorption and membranes.
A system based on 1,1,3,3-tetramethyl guanidine (TMG) in
6.5. CO2 capture and monitoring combination with ethylene glycol (EG) in DMSO was designed
Fennell et al.262 have recently written a comprehensive review for cellulose dissolution by CO2 capture.264 After bubbling CO2,
on leading CO2 capture technologies such as amine scrubbing, the solution created a new solvent that accomplished the

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Fig. 90 Synthesis of copolymer bearing N-heterocyclic carbene.265
Reproduced from ref. 265 with permission from ACS publications.
dissolution of up to 10 wt% of cellulose in mild conditions. The
interactions of the hydroxyl groups in cellulose with the in situ
formed carbonate anions was proposed to act as a driving force for
cellulose dissolution in prepared solvent under mild conditions.264
An N-heterocyclic carbine-functionalized polymer was synthesized
as a highly efficient selective adsorbent for reversible fixation-
release of CO2.265 The synthesized polymer (Fig. 90) could react
rapidly with CO2 to produce zwitterionic adducts at temperatures
between 20 and 100 1C. The trapped CO2 was released by a N2
flow at 140 1C.
Furusho and Endo266 investigated the CO2 capture and release
of an aliphatic polyamidine with hexamethylene linker in solution
and solid state. They have explored the difference in CO2 capture
and release between this polyamidine and polyethyleneimine, and
common polyamines. Due to the cumbersome process of synthe-
sizing the polymer, they synthesized copolymers bearing DBU and
DBN (1,5-diazabicyclo[4.3.0]-non-5-ene) moieties for CO2 capturing
from air.18 The synthesized copolymers trap CO2 at 25 1C and
release it at 120 1C by bubbling N2. Also, they concluded that
monocyclic amidines can fix CO2 in dry conditions and are
converted to the corresponding bicarbonates via hydrolysis of
the zwitterionic adducts.19
PDMAEMA conjugated with a fluorescent-sensitive group, a
perylene-3,4,9,10-tetracarboxylic acid bisimide (PBI) fluorophore,
was prepared via ATRP for detection of dissolved CO2 in aqueous
media by colorimetric and fluorescent measurements.20 The
colour and fluorescence emission of the aqueous polymer
solution changed in response to the presence of dissolved CO2.
All the changes were reversible upon addition and removal of
CO2 (Fig. 91). One potential application of this system could be
in water quality analysis and visual detection of CO2 diffusing in
an aqueous medium.20
A smart copolymer containing an amidine group, poly(dimethyl
acrylamide-co-(N-amidino)ethylacrylamide) or p(DMA-co-NAEAA),
was prepared by FRP and employed for dissolved CO2 (dCO2)
detection.21 The amidine group of the polymer could be protonated
by capturing H+ dissociated by the dCO2, and aggregate gold
nanoparticles by the electrostatic interaction between the positive
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Fig. 91 Reversible adsorption and desorption (purging with N2) of CO2 in
the aqueous solution of PBI–PDMAEMA (containing two arms of
PDMAEMA and a centre PBI unit) showing the reversible fluorescence
‘‘turn-on’’ and ‘‘turnoff’’ response.20 Reprinted from ref. 20 with permission
from the RSC.
charge of the amine groups of the polymer and the negative-charged
gold nanoparticles. This aggregation causes a colour change of the
solution from red to blue.21 Therefore, the concentration of dCO2
can be monitored by observing the colour change in the solution or
by measuring the UV absorbance change of the solution of gold
nanoparticles.21
Zhou et al. synthesized porous polymer networks (PPNs)
containing amines for CO2 capture.22,23 These polymers exhibited
significant CO2 capturing capacities at low pressures, and consider-
able CO2/N2 adsorption selectivities at room temperature. The trend
in the improvement of CO2 adsorption of PPNs was DETA > TAEA >
TETA > EDA. In fact, PPN-6-CH2DETA exhibited a higher selectivity
for CO2 than any other porous material reported so far (PPN-6 is the
support structure and contains a covalently bonded carbon scaffold
with a Brunauer–Emmett–Teller (BET) surface area of 4023 m2 g1).
In addition to high selectivity and high CO2 capacity, these polymers
have physicochemical stability and low regeneration costs, which
make them ideal for post-combustion CO2 capture technology.22
Acylated branched polyethyleneimine, as the first thermo-
sensitive commercially available polymer, was used as an
efficient tool for CO2 release.267 The capability of the acrylated
thermosensitive branched polyethyleneimine was low, but due
to the LCST behaviour of the polymer, its CO2 desorption
performance improved.
In addition to adsorption, membranes are also commonly
used for CO2 separation, and can be categorized as three types
of polymeric, inorganic, or facilitated transport membranes.268
In a facilitated transport membrane, a carrier of gas molecules
reacts chemically and reversibly with the characteristics gas
molecules like CO2 in the mixed gas. CO2 molecules are then
transported from one side with high potential energy to the other
side with low potential energy through the membranes.268 It has
been shown that after thermal annealing of PS-b-PEO, to obtain
worm-like morphologies, and then hydrogen bonding with amidine
groups as guest molecules, the resultant supramolecular
assembly can be used for CO2 separation.268 As shown in Fig. 92,
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Fig. 93 Schematic illustration of the chemical principles of CO2-switchable

worm-like micelles based on ODPTA.33 Reprinted from ref. 33 with permission
from the RSC.

result, a higher concentration is required for the self-assembly

Fig. 92 The chemical structure of the PS-b-PEO with hydrogen boning
of ‘‘ODPTA–HCl’’.33 Furthermore, electrostatic repulsive forces
to the guest amidine molecule M (top), and preparation of PS-b-PEO/M
membrane and the model proposed for the nanostructured membrane
between ionic head groups are less efficiently screened compared to
(bottom).268 Reprinted from ref. 268. ion pairs. Therefore, the formation of WLMs is not favoured.33 This
study showed that CO2 can be employed as an environmentally-
benign trigger to perform a reversible ‘‘sol–gel’’ transition in a one-
the intermediate compound is delivered from the side with high component dispersion based on the formation and dissociation of
potential energy to the side with low potential energy and then SWLM of the long chain polyamine surfactant ODPTA (Fig. 93). The
amidine molecules and CO2 are released from the intermediate viscoelasticity of the solution can be reversibly switched ‘‘on’’ and
compound at the low potential energy side.268 ‘‘off’’ over several repeatable cycles by alternating addition and
removal of CO2.33
6.6. CO2-switchable worm-like micelles (SWLM) A SWLM system was prepared without any hydrotropes and
only by employing N-erucamidopropyl-N,N-dimethylamine.34
Feng’s group has performed several studies in the area of CO2- Hydrotropes are small organic water-molecules that are added to
switchable worm-like micelles.32–36 Theoretically, block copoly- the aqueous solution of amphiphiles to increase the formation of
mers self-assemble to spherical micelles when fphilic > 50%, worm-like micelles by reducing the distances between amphi-
worm-like micelles when 40% o fphilic o 50%, vesicles when philes.269 The transition from sol to gel occurs at room temperature
25% o fphilic o 40%, and planar structures when fphilic o 25%.28 and pressure without need to use heat or any inert gas (Fig. 94).
Worm-like micelles are sometimes called ‘‘living’’ or ‘‘equilibrium’’ The CO2-switchability of this system was further investigated by
polymers because unlike the chain entanglement in polymers, they rheological measurements. Steady-state measurements confirmed
can break and recombine.35 that, when switched on, the SWLMs exhibits shear-thinning
A mixture of the commercially available anionic surfactant behaviour at shear rates higher than critical shear rate. Also,
SDS and N,N,N 0 ,N 0 -tetramethyl-1,3-propanediamine (TMPDA) oscillatory data prove that storage modulus (G 0 ) is far above the
with a molar ratio of 2 : 1 led to the formation of CO2-
switchable WLMS.32 When CO2 is added to an aqueous mixture
of these reactants, the tertiary amines of the TMPDA molecules
are protonated and converted to the quaternary ammonium
species. Therefore, they make a bridge to SDS molecules by
electrostatic attraction forces. In this state they behave as a
pseudogemini surfactants and form viscoelastic WLMS. By the
removal of CO2, the quaternized species are deprotonated to
the original tertiary amines. Thus, the conventional SDS mole-
cules are attained again and low-viscosity spherical micelles
result.32
A SWLM system was developed by employing a C18-tailed
polyamine surfactant (octadecyl dipropylene triamine, ODPTA)
that undergoes a fully repeatable and reversible ‘‘sol–gel’’
transition upon the stimulation of CO2 and N2.33 HCl also
protonates ODPTA but the counterions CO32 or HCO3 are Fig. 94 Schematic illustration of the chemical principles governing
less hydrated than Cl. Thus ‘‘ODPTA-HCl’’ increases the CO2–air switchable worm-like micelles.34 Reprinted from ref. 34 with
solubility of the surfactant compared to ‘‘ODPTA–CO2’’. As a permission from the RSC.

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Fig. 95 Rheological measurements of UC22AMPM solution (100 mM
at 25 1C). Left: Flow curves of UC22AMPM before and after bubbling
CO2 and air (0.1 MPa) at ambient temperature; right: dynamic rheology of
UC22AMPM aqueous solution in the presence of CO2.34 Reprinted from
ref. 34 with permission from the RSC.
loss modulus (G00 ) over a broad range of frequencies, which is
typical of viscoelastic fluids (Fig. 95).
A CO2-switchable anionic worm-like micellar system was
fabricated based on natural erucic fatty acid.35 This system is
simple to obtain compared with other CO2-switchable worm-
like micelles because only changing the pH of the erucic acid
solution is required; there is no need for adding hydrotropes or
complex organic synthesis.35 The formation of SWLMs is due to
the self-assembly of sodium erucate.270 A mixture of N,N-dimethyl-
oleoaminde-propylamine (DOAPA) and sodium p-toluene sulfo-
nate (SPTS) with the molar ratio of 1 : 1 produced SWLMs.271
The electrostatic attraction between positive charges of the
quaternary ammonium and negative charges of the SPTS
creates self-assemblies and formation of a viscoelastic worm-
like fluid. However, upon the removal of CO2, the quaternary
ammonium is deprotonated and returns to the original state of
the tertiary amines. Therefore, the assemblies are split which
leads to the formation of a water-like fluid.271
SWLMs made by the self-assembly of CO2-switchable triblock
copolymers comprised of a CO2-switchable interior core PDEAEMA
(A), middle hydrophobic PS (S), and hydrophilic outer layer of PEO
(O) were transformed to straight nanowires upon exposure to CO2
and back to the original SWLMs after the removal of CO2.31 It was
shown that the synergy of core-chain restricted hydration and
corona-chain repulsion is a driving force for deformation of block
copolymer assemblies upon the stimulus of CO2.31
CO2-switchable viscoelastic worm-like micelles were pre-
pared from solutions of 2-(dimethylamino) ethanol (DMAE)
and sodium octadecyl sulfate in the presence of CO2.269 When
CO2 is removed by N2 bubbling, the viscosity of the solution
decreases and it becomes comparable to that of pure water
(Fig. 96). The formation of worm-like micelles was confirmed by
cryo-TEM (Fig. 97). It was shown that that the solution of
sodium stearate and sodium nitrate behaves in an opposite
way and it has high viscosity only if CO2 is absent.
A framework of worm-like micelles was prepared by the
reaction of compressed CO2 and hexadecylamine in water.272
The key parameter in the formation of mesoporous silica is the
cationic surfactants (formed in situ), which act as mesostructure-
directing templates. It has also been shown that CTAB–sodium
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Fig. 96 (a) Alternating increase and decrease in the zero-shear viscosity
of the aqueous solution of sodium octadecyl sulfate (200 mM) and DMAE
(200 mM) by bubbling CO2 and N2 at 1 bar and 60 1C due to switching the
DMAE between cationic and neutral states. (b) The initial solution was
prepared by addition of the sodium octadecyl sulfate to 100 mL distilled water
followed by mechanical agitation for several minutes at 60 1C. The viscosity of
the prepared solution was 1.1 mPa s. After adding the DMAE, the viscosity
increased a little bit to 1.2 mPa s. However, after bubbling CO2 for 15 min at
60 1C, the solution turned into a gel with a viscosity of 26 200 mPa s. (c) The
viscosity returned to its original value (1.2 mPa s) after sparging N2 for 50 min at
60 1C. Zero-shear viscosity was acquired by extrapolating the viscosity curve
along the plateau in the Newtonian region to zero shear rate.269 Reprinted
from ref. 269 with permission from the RSC.
Fig. 97 The cryo-TEM image of the mixture sodium octadecyl sulfate
(200 mM) and DMAE (200 mM).269 Reprinted from ref. 269 with permission
from the RSC.
salicylate (NaSal) worm-like micelles are formed with CO2 bub-
bling in the presence of TEA as a CO2-responsive group without
needing any organic synthesis.273 This system can reversibly
change between a water-like solution and a viscoelastic fluid
up to 15 cycles with alternating treatments of CO2 and N2.
A linear ABC triblock copolymer comprised of a PEO hydro-
philic block (O), poly(2,2,3,4,4,4-hexafluorobutylmethacrylate)
(F), and PDEAEMA (E), synthesized by RAFT polymerization,
showed a morphological transition in water/ethanol solvent
with variation in the volume ratio of water.213 When the water
volume fraction decreases from 0.50 to 0, the morphology of the
triblock copolymer varies from WLMs to long cylinders, then to
short rods to finally to spheres. It was observed that preformed
WLMs do not fully change to spheres even at 95% protonation
degree of the PDEAEMA block, which was attributed to the
increasing interfacial tension of the solvent and fluorinated
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blocks due to the strictly packed arrangement of the fluorinated
block.
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6.7. Other applications
6.7.1. Forward osmosis desalination. Forward osmosis extracts
clean water from seawater or wastewater through a semipermeable
membrane into a draw solution. The draw solution is a highly
concentrated aqueous solution of an easily removed salt. An ideal
draw solute should create high osmotic pressure and be easily
removed after the osmosis, leaving behind the fresh water. Ideally,
it would not be toxic, not degrade the membrane, and produce
negligible back diffusion to the feed solution. A CO2-switchable
polymer as a draw solute was detailed in a 2010 patent applica-
tion.26 The draw solution would be a solution of the bicarbonate
salt of such a polymer in carbonated water. After water has passed
through the membrane from the seawater or wastewater to the
draw solution by forward osmosis, then the CO2 can be removed by
bubbling of air or nitrogen (Fig. 98). The neutral polymer, if
insoluble, would precipitate and be removed by filtration, and if
soluble would be removed by reverse osmosis. The reverse osmosis
step would not be too energy intensive because the neutral polymer
would have low osmotic pressure. Removal of the polymer leaves
fresh water ready for use.
In particular, Jessop et al. suggested the use of PDEAEMA
because, in its neutral form, it is insoluble in water and can be
therefore be recovered easily. Similarly PDMAEMA was later
employed as a draw solute for forward osmosis (FO) desalina-
tion.27 When PDMAEMA is protonated by bubbling CO2, the
solute retains sufficiently high osmolality and produces a large
water flux in the FO process (Fig. 99). PDMAEMA can be easily
removed from the water by precipitation by CO2 removal and
application of moderate heat to reach a temperature at which
the polymer is insoluble. Such polymeric draw solutes have
remarkably low back diffusion, no degradation effects on the
FO membrane and low toxicity.
Jiang et al. developed a CO2-responsive ion channel device in
which both entrances were covered by a polymeric film containing
PDEAEMA brushes.209 The gas-breathing polymer film on the
channel membrane was repeatedly transformed from hydro-
phobic to hydrophilic state upon addition and removal of CO2.
Fig. 98 A concentrated solution of polymeric amine, in its bicarbonate
form in carbonated water, can serve as a draw solution for the forward
osmosis recovery of fresh water from sea water or wastewater.26
4428 | Chem. Soc. Rev., 2016, 45, 4391--4436
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Fig. 99 Schematic diagram of the dual responsive draw solute for for-
ward osmosis desalination.27 Reprinted from ref. 27 with permission from
the RSC.
Therefore this smart polymer-coated channel, independently
from voltage polarity, can be in the closed (off) or open (on)
status and could have potential applications in the field of
energy, sample filtration and seawater desalination (Fig. 100).
6.7.2. Separation. Separation processes are the main step
of many chemical industries and traditionally are performed by
extraction, distillation, crystallization, membrane transport
processes, and chromatography.
However, molecular receptors are becoming more important
in separation technology.274 Separation by molecular recogni-
tion still has some problems including breaking or dissociation
of the ‘‘host–guest’’ complexes upon separation, and the use of
large quantities of toxic solvents.274 Alternatively, separation
can be done by combination of selective complexation by
CO2-switchable macrocyclic receptors and then CO2-triggered
precipitation of the complexes. In this technique, receptors that
contain primary amino groups and capable of switching by CO2
are complexed with target species and then CO2 is introduced
(room temperature, 1 atm) to react with the amino groups of
the receptors. Thus, crosslinked carbamates are produced and
precipitate.274 If target complexes are incorporated within
their structures, the process will separate them from the bulk
Fig. 100 (A) Schematic demonstration of the ‘‘on’’ and ‘‘off’’ states of a
cylindrical channel covered by a CO2-responsive polymer films. (B) The
extended status due to the protonation and the collapsed status due to the
deprotonation of the polymer film.209 Reprinted from ref. 209 with
permission from the RSC.
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Fig. 102 A CO2-switchable drying agent to which water could bind in

three ways: (a) by reacting with the amine to form the bicarbonate salt (b)
by adhesion to the support (shown as a pink band), and (c) as waters of
hydration of the salt ions (shown as a blue band).131 Reprinted from ref. 131
with permission from the RSC.
Fig. 101 Experimental approaches employed in the separation of the
a-tocopherol from its tocopherol homologues and recovery of the extractant.24
Reprinted from ref. 24 with permission from ACS publications. were as low as 10 ppm. The presence of CO2 was essential to
achieve flocculation and coagulation of the fine particles.
Pyrene-containing CO2-switchable polymers were used to
solution and uncomplexed species. The precipitated materials
control the dispersion of SWNTs by combining p–p adsorption
can be separated and CO2 is released upon heating or the
and the electrostatic interaction in immiscible mixed solvents by
addition of acid. As a result, the precipitated materials dissociate
bubbling and removing CO2.212 The modified SWNT nano-hybrids
back to monomers and the complexed species are released in
could undergo facile hydrophobic–hydrophilic transitions upon the
their pure form.274
stimulation with CO2. Due to the noncovalent p–p modification,
The extraction of a-tocopherol from the tocopherol homologues
the CO2 stimulus contaminates neither the tubes nor dispersed
using polyethyleneimine (PEI) as a CO2-switchable polymeric
media; therefore these reversibly dispersible SWNTs can be used in
extractant has been investigated.24 Different PEI–cosolvent
biological applications.212
solutions were employed to separate tocopherols from their
6.7.4. Encapsulation. CO2-responsive capsules were obtained
hexane solutions. An obvious advantage of PEI extraction is its
by doping standard poly(diallyldimethylammonium chloride)/
CO2-switchability.24 PEI-extracted tocopherols are replaced and
poly(styrenesulfonate), PDDA/PSS, capsule walls with oligoamine II
separated from PEI chains upon introduction of CO2. PEI–CO2 is
(shown in Fig. 103). Non-cytotoxic oligoamine ‘‘patches’’ composed
precipitated and separated from the extract phase, which signifi-
of exactly 11 amine groups switch in the ordinary pH range
cantly facilitates the reverse extraction of tocopherols and the
(5.5–7.5) between cationic and anionic via interaction with CO2
retrieval of PEI for reuse (Fig. 101). Precipitated PEI–CO2 can be
and carbamate formation.25 The switching process is completely
redissolved in the cosolvent phase for reuse by heating and N2
reversible, therefore it can be employed for the chemical ‘‘gating’’
bubbling.24
of structures. Polyelectrolyte capsules comprised of these patches
Used solvents are usually contaminated with water, altering
as structural interlayers exhibit stable architecture, but after
their properties for some industrial processes, therefore, separ-
bubbling CO2, a reversible expansion that acts as a gating
ating water from (i.e. drying) organic liquids is a very important
of the permeation for large hydrophilic polymeric species
operation in many industrial processes like solvent recycling
and also the production of ethanol and biodiesel.131 An ideal
drying agent should be able to bind water strongly during the
capture stage and release it easily during regeneration. Addi-
tionally, the drying agent should be easily recycled as well as
inert to the solvent of interest and have a high capacity for
absorbing water.131 Based on these criteria, our group recently
developed a CO2-switchable drying agent containing tertiary
amine groups and evaluated it for the drying of isobutanol.131
Silica particles with PDMAPMAm chains grafted to the surface
by SI-ATRP were used to dry solvents; the water content of wet
isobutanol was reduced by 490 mg per gram of drying agent
after application of CO2 (Fig. 102).
6.7.3. Controlling dispersion of non-switchable materials.
Several CO2-switchable polymers such as amino-functionalized
Fig. 103 Synthetic route for preparing the oligoamine II (conditions:
PMMA were designed and employed for water purification (i) methanol-N,N0 -diisopropylcarbodiimide), 0 1C, 24 h; (ii) methanol-N,N0 -
applications and showed effective performance in the settling diisopropylcarbodiimide, 0 1C, 24 h; (iii) trifluoroacetic acid–H2O, 90 min.25
of fine particles in the presence of CO2.189 The polymer loadings Reprinted from ref. 25 with permission from the RSC.

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(e.g. 70 kDa dextran) is observed.25 This system may have possible

applications for the encapsulation and release of various
compounds.25
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A novel strategy for releasing encapsulated solutes from

liposomes was presented by incorporating the lipophilic pro-
surfactant into carboxyfluorescein (CF) loaded liposomes.275
A decrease in pH due to CO2 bubbling presumably leads to the
protonation of the surfactant and as a result expansion of the
bilayer and the release of CF.275 Incorporation of an amidine
group in the structure of a diblock copolymer could generate
‘‘breathing’’ vesicles which expand and contract upon addition
and removal of CO2.29 These nanocapsules can be employed in
the controlled release of organic substrates with the stimula-
tion of CO2.
6.7.5. Biopolymers. Chitin, the most abundant polysac-
charide, is composed of a chain of b-(1 - 4)-linked N-acetyl-
D-glucosamine residues, and is naturally available in the
exoskeletons of insects, crustaceans, and shellfish.276 The main Fig. 104 Schematic illustration of (a) the preparation of CNC–APIm and
problem with chitin is its insolubility in common organic (b) CO2-switchability of CNC–APIm.277
solvents and water. Nanofibrillation is a common method for
making chitin-based functional materials. However since chitin
increases considerably the stress and creates fractures in highly
has many hydroxyl groups in its backbone, the dispersed state in wet
impermeable igneous rock and in an enhanced geothermal
conditions is prone to agglomeration due to strong hydrogen
reservoir (which is a confined environment). The efficiency of
bonding. Nanofibrillation from dried chitin agglomerates is difficult
this system is higher than conventional fracturing fluids.
to achieve.276 It has been shown that functionalization of chitin
6.7.7. Membranes. Yuan’s group developed CO2-switchable
with amidine groups can facilitate the nanofibrillation of chitin
nanofibrous membranes, which were capable of switching oil/
even after agglomeration by drying.276 Amidine-derivatives of
water wettability.122 To induce CO2-responsiveness in the nano-
chitin are converted to amidinium chitin by bubbling of CO2 and
structured electrospun polymer membranes, DEAEMA was used
ultrasonication in water, which show agglomeration–nanofibrillation
in the synthesis of PMMA-co-PDEAMA and then this copolymer
transition behaviour after mixing with water and drying with N2
was converted to the polymeric nanofibers using electrospinning.
bubbling followed by ultrasonication.276 After deprotonation of
It is well-known that electrospun nanofibrous membranes are
the amidinium chitin by base, agglomeration occurs and the
suitable for preparing smart surface materials because of their
produced amidinated chitin forms the nanofiber network again
large surface-to-volume ratio and high porosity.122
by re-protonation via CO2 bubbling and ultrasonication in
water.276
Cellulose nanocrystals (CNCs), which are produced by acid 7. Conclusion and perspective
hydrolysis of cellulose sources, are biodegradable with low density,
high specific surface area, and unique mechanical and optical CO2-switchable polymers have become established as a new
properties.277 Our group modified CNCs by a one-step coupling innovative and valuable class of stimuli-responsive polymers. Offer-
reaction with 1-(3-aminopropyl)imidazole (APIm) mediated by ing the advantages of benign triggers that are easily administered
1,10-carbonyldiimidazole (CDI). The modified CNCs (CNC–APIm) and removed from the system of interest with low environmental
were CO2-switchable and could be easily dispersed into carbonated impact and toxicity, they are likely to become increasingly utilized for
water, however, bubbling N2 into the dispersion led to the formation a range of applications, as demonstrated in this review. Much has
of aggregates due to the presence of the CO2-responsive, chemically been learned about the fundamental principles of synthesizing
bonded, and stable imidazole groups on the surface of CNCs polymers to exhibit CO2-switchability, including the choice of switch-
(Fig. 104). able moiety (largely dependent on the demands of the application of
6.7.6. Enhanced geothermal systems. The main challenge interest) and how effective the switching process can be expected to
in the use of enhanced geothermal systems (EGS), as an important be under the conditions of interest.
alternative for renewable energy production, is low efficiency because The number of monomers that exhibit effective CO2-switchability
of the lack of sustained production, which is attributed to the high is still somewhat limited. Expanding this selection would provide
fluid flow rates required and the significant amounts of fractured- greater versatility in designing CO2-switchable polymeric structures.
rock surface area for heat exchange.278 To address these issues, In published work to date, CO2-switchability has mostly been
Jung et al. developed a non-toxic CO2-switchable and rheoreversible assessed somewhat simply as occurring or not occurring as
fracturing polymer aqueous solution (a polyallylamine (PAA)–CO2 evidenced by an observed change in behaviour or properties. In
fracturing fluid) that undergoes a reversible volume expansion and fact the situation is often more complex, with varying degrees of
contraction upon addition and removal of CO2.278 This system protonation/deprotonation (‘‘switching’’) occurring depending

4430 | Chem. Soc. Rev., 2016, 45, 4391--4436 This journal is © The Royal Society of Chemistry 2016

Chem Soc Rev
on the local environment (e.g. hydrophilic versus hydrophobic),
temperature, pKaH values of the functional groups, or the
presence of other substances in the system (particularly acids
Published on 10 June 2016. Downloaded by INDIAN INSTITUTE OF TECHNOLOGY BOMBAY on 2/2/2022 11:49:32 AM.
and bases but also for example electrolytes) that can dramatically
impact the effectiveness of the switching process. Quantitative
measurement of the % protonation of individual polymers under
the conditions of interest is needed. Another poorly understood
concern is the effect of mass transfer (gas diffusion) limitations
on rate in the switching process, which can be influenced by
both the solubility of the gas (CO2, N2, Ar, air) and its ability to
diffuse through the polymeric structure and environment to the
switchable groups. Long term degradation of switching perfor-
mance of materials designed to be switchable over numerous
cycles (perhaps thousands or millions) has not been addressed
but will be critical for the successful development of devices or
sensors.
Looking forward, we believe there will be an increasing focus
on the development of new applications and further refinement
of recently developed materials targeted at new applications.
Due to ease of selecting and polymerizing monomers with
CO2-switchable groups, or alternatively functionalizing polymers,
polymer particles or polymer surfaces to impart CO2-switchability,
progress could be rapid with a plethora of new stimuli-responsive
materials becoming available in the near future.
Acknowledgements
Support from the Natural Sciences and Engineering Research
Council of Canada (NSERC), the Canada Research Chairs Program
(PGJ) and the Ontario Research Chairs Program (MFC) is gratefully
acknowledged.
Notes and references
1 Q. Zhang, G. Yu, W. Wang, H. Yuan, B. Li and S. Zhu,
Langmuir, 2012, 28, 5940–5946.
2 P. G. Jessop, S. M. Mercer and D. J. Heldebrant, Energy
Environ. Sci., 2012, 5, 7240–7253.
3 S. Lin and P. Theato, Macromol. Rapid Commun., 2013, 34,
1118–1133.
4 A. I. Cooper and J. M. DeSimone, Curr. Opin. Solid State
Mater. Sci., 1996, 1, 761–768.
5 J. Nicolas, Y. Guillaneuf, C. Lefay, D. Bertin, D. Gigmes and
B. Charleux, Prog. Polym. Sci., 2013, 38, 63–235.
6 J. Jennings, M. Beija, A. P. Richez, S. D. Cooper,
P. E. Mignot, K. J. Thurecht, K. S. Jack and S. M. Howdle,
J. Am. Chem. Soc., 2012, 134, 4772–4781.
7 Y. Liu, P. G. Jessop, M. F. Cunningham, C. A. Eckert and
C. L. Liotta, Science, 2006, 313, 958–960.
8 C. I. Fowler, C. M. Muchemu, R. E. Miller, L. Phan,
C. O’Neill, P. G. Jessop and M. F. Cunningham, Macro-
molecules, 2011, 44, 2501–2509.
9 M. Mihara, P. G. Jessop and M. F. Cunningham, Macro-
molecules, 2011, 44, 3688–3693.
This journal is © The Royal Society of Chemistry 2016
View Article Online
Review Article
10 C. I. Fowler, P. G. Jessop and M. F. Cunningham, Macro-
molecules, 2012, 45, 2955–2962.
11 X. Su, P. G. Jessop and M. F. Cunningham, Macromolecules,
2012, 45, 666–670.
12 J. Pinaud, E. Kowal, M. F. Cunningham and P. G. Jessop,
ACS Macro Lett., 2012, 1, 1103–1107.
13 D. Gariepy, Q. Zhang and S. Zhu, Macromol. Chem. Phys.,
2015, 216, 561–568.
14 D. Han, O. Boissiere, S. Kumar, X. Tong, L. Tremblay and
Y. Zhao, Macromolecules, 2012, 45, 7440–7445.
15 Y. Hoshino, K. Imamura, M. Yue, G. Inoue and Y. Miura,
J. Am. Chem. Soc., 2012, 134, 18177–18180.
16 D. Nagai, A. Suzuki and T. Kuribayashi, Macromol. Rapid
Commun., 2011, 32, 404–410.
17 A. J. Morse, S. P. Armes, K. L. Thompson, D. Dupin,
L. A. Fielding, P. Mills and R. Swart, Langmuir, 2013, 29,
5446–5475.
18 B. Ochiai, K. Yokota, A. Fujii, D. Nagai and T. Endo,
Macromolecules, 2008, 41, 1229–1236.
19 N. Aoyagi, Y. Furusho, Y. Sei and T. Endo, Tetrahedron,
2013, 69, 5476–5480.
20 L. Q. Xu, B. Zhang, M. Sun, L. Hong, K.-G. Neoh, E.-T. Kang
and G. D. Fu, J. Mater. Chem. A, 2013, 1, 1207–1212.
21 Y. Ma and L. Y. L. Yung, Anal. Chem., 2014, 86, 2429–2435.
22 W. Lu, J. P. Sculley, D. Yuan, R. Krishna, Z. Wei and
H. C. Zhou, Angew. Chem., Int. Ed., 2012, 51, 7480–7484.
23 W. Lu, J. P. Sculley, D. Yuan, R. Krishna and H.-C. Zhou,
J. Phys. Chem. C, 2013, 117, 4057–4061.
24 G. Yu, Y. Lu, X. Liu, W.-J. Wang, Q. Yang, H. Xing, Q. Ren,
B.-G. Li and S. Zhu, Ind. Eng. Chem. Res., 2014, 53, 16025–16032.
25 L. Hartmann, M. Bedard, H. G. Börner, H. Möhwald,
G. B. Sukhorukov and M. Antonietti, Soft Matter, 2008, 4,
534–539.
26 P. G. Jessop, S. M. Mercer, T. Robert, R. S. Brown, B. E.
Mariampillai, R. Resendes and D. S. Wechsler, Systems and
Methods for Use of Water with Switchable Ionic Strength,
PCT/CA2011/050777, 2011, and US 2014/0076810 A1.
27 Y. Cai, W. Shen, R. Wang, W. B. Krantz, A. G. Fane and
X. Hu, Chem. Commun., 2013, 49, 8377–8379.
28 A. Feng, C. Zhan, Q. Yan, B. Liu and J. Yuan, Chem.
Commun., 2014, 50, 8958–8961.
29 Q. Yan, R. Zhou, C. Fu, H. Zhang, Y. Yin and J. Yuan,
Angew. Chem., Int. Ed., 2011, 50, 4923–4927.
30 Q. Yan, J. Wang, Y. Yin and J. Yuan, Angew. Chem., Int. Ed.,
2013, 52, 5070–5073.
31 Q. Yan and Y. Zhao, J. Am. Chem. Soc., 2013, 135,
16300–16303.
32 Y. Zhang, Y. Feng, Y. Wang and X. Li, Langmuir, 2013, 29,
4187–4192.
33 Y. Zhang, Y. Feng, J. Wang, S. He, Z. Guo, Z. Chu and
C. A. Dreiss, Chem. Commun., 2013, 49, 4902–4904.
34 Y. Zhang, Z. Chu, C. A. Dreiss, Y. Wang, C. Fei and Y. Feng,
Soft Matter, 2013, 9, 6217–6221.
35 Y. Zhang, H. Yin and Y. Feng, Green Mater., 2014, 2, 16–20.
36 Z. Chu, C. A. Dreiss and Y. Feng, Chem. Soc. Rev., 2013, 42,
7174–7203.
Chem. Soc. Rev., 2016, 45, 4391--4436 | 4431

Review Article
37 E. R. Moore and N. A. Lefevre, Method for Shear Coagulation
of Latex Resins, US Pat., 4,623,678, 1986.
38 H. Xu and D. M. Rudkevich, J. Org. Chem., 2004, 69,
Published on 10 June 2016. Downloaded by INDIAN INSTITUTE OF TECHNOLOGY BOMBAY on 2/2/2022 11:49:32 AM.
8609–8617.
39 H. Xu and D. M. Rudkevich, Chem. – Eur. J., 2004, 10,
5432–5442.
40 E. Carretti, L. Dei and R. G. Weiss, Soft Matter, 2005, 1,
17–22.
41 P. G. Jessop, Reversibly Switchable Surfactants and Methods
of Use Thereof, US Pat., 8,283,385, 2012.
42 Q. Yan and Y. Zhao, Chem. Commun., 2014, 50, 11631–11641.
43 H. Wei, S.-X. Cheng, X.-Z. Zhang and R.-X. Zhuo, Prog.
Polym. Sci., 2009, 34, 893–910.
44 Z. M. O. Rzaev, S. Dincer and E. Piskin, Prog. Polym. Sci.,
2007, 32, 534–595.
45 E. Gil and S. Hudson, Prog. Polym. Sci., 2004, 29,
1173–1222.
46 H. Almeida, M. H. Amaral and P. Lobão, J. Appl. Pharm.
Sci., 2012, 2, 1–10.
47 C. Weber, R. Hoogenboom and U. S. Schubert, Prog. Polym.
Sci., 2012, 37, 686–714.
48 F. Liu and M. W. Urban, Prog. Polym. Sci., 2010, 35, 3–23.
49 A. S. Carreira, F. A. M. M. Gonçalves, P. V. Mendona,
M. H. Gil and J. F. J. Coelho, Carbohydr. Polym., 2010, 80,
618–630.
50 A. Arnone, Nature, 1974, 247, 143–145.
51 M. Dixon and B. Sciences, J. Appl. Bacteriol., 1989, 67,
109–136.
52 C. Bastioli, Handbook of Biodegradable Polymers, Rapra
Technology Limited, United Kingdom, 2005.
53 S. Dai, P. Ravi and K. C. Tam, Soft Matter, 2009, 5, 2513–2533.
54 X. Su, T. Robert, S. M. Mercer, C. Humphries, M. F.
Cunningham and P. G. Jessop, Chem. – Eur. J., 2013, 19,
5595–5601.
55 Y. Zhao and J. He, Soft Matter, 2009, 5, 2686–2693.
56 O. Kuksenok, P. Dayal, A. Bhattacharya, V. V Yashin,
D. Deb, I. C. Chen, K. J. Van Vliet and A. C. Balazs, Chem.
Soc. Rev., 2013, 42, 7257–7277.
57 H. Cho, J. Bae, V. K. Garripelli, J. M. Anderson, H.-W. Jun
and S. Jo, Chem. Commun., 2012, 48, 6043–6045.
58 Y. A. Gan Liu, R. Ma, J. Ren, Z. Li, H. Zhang, Z. Zhang and
L. Shi, Soft Matter, 2013, 9, 1636–1644.
59 P. Schattling, F. D. Jochum and P. Theato, Polym. Chem.,
2014, 5, 25–36.
60 R. P. Shaikh, V. Pillay, Y. E. Choonara, L. C. du Toit, V. M. K.
Ndesendo, P. Bawa and S. Cooppan, AAPS PharmSciTech,
2010, 11, 441–459.
61 D. Han, X. Tong and Y. Zhao, ACS Macro Lett., 2012, 1, 57–61.
62 B. Chang, X. Sha, J. Guo, Y. Jiao, C. Wang and W. Yang,
J. Mater. Chem., 2011, 21, 9239–9247.
63 X. Tang, X. Liang, L. Gao, X. Fan and Q. Zhou, J. Polym. Sci.,
Part A: Polym. Chem., 2010, 48, 2564–2570.
64 J. Y. Choi, J. Y. Kim, H. J. Moon, M. H. Park and B. Jeong,
Macromol. Rapid Commun., 2014, 35, 66–70.
65 L. M. Scott, T. Robert, J. R. Harjani and P. G. Jessop, RSC
Adv., 2012, 2, 4925–4931.
4432 | Chem. Soc. Rev., 2016, 45, 4391--4436
View Article Online
Chem Soc Rev
66 J. Y. Quek, P. J. Roth, R. A. Evans, T. P. Davis and A. B.
Lowe, J. Polym. Sci., Part A: Polym. Chem., 2013, 51, 394–404.
67 J. Y. Quek, T. P. Davis and A. B. Lowe, Chem. Soc. Rev.,
2013, 42, 7326–7334.
68 J. R. Harjani, C. Liang and P. G. Jessop, J. Org. Chem., 2011,
76, 1683–1691.
69 T. W. Graham Solomons and C. B. Fryhle, Organic Chemistry,
John Wiley & Sons, Inc., 9th edn, 2008.
70 A. Darabi, A. R. Shirin-Abadi, J. Pinaud, P. G. Jessop and
M. F. Cunningham, Polym. Chem., 2014, 5, 6163–6170.
71 E. Ceschia, J. R. Harjani, C. Liang, Z. Ghoshouni, T. Andrea,
R. S. Brown and P. G. Jessop, RSC Adv., 2014, 4, 4638–4645.
72 Q. Wang, S. Fu and T. Yu, Prog. Polym. Sci., 1994, 19,
703–753.
73 G. Odian, Principles of Polymerization, John Wiley & Sons,
Hoboken, New Jersey, 4th edn, 2004.
74 N. Shirakbari, M. Ebrahimi, H. Salehi-Mobarakeh and
M. Khorasani, J. Macromol. Sci., Part B: Phys., 2014, 53,
1286–1292.
75 M. J. Monteiro, M. Sjöberg, J. van der Vlist and C. Göttegens,
J. Polym. Sci., Part A: Polym. Chem., 2000, 38, 4206–4217.
76 E. Aramendia, J. Barandiaran, J. Grade, T. Blease and
M. Asua, Langmuir, 2005, 21, 1428–1435.
77 Q. Zhang, G. Yu, W. Wang, H. Yuan, B. Li and S. Zhu,
Macromolecules, 2013, 46, 1261–1267.
78 P. Brown, C. P. Butts and J. Eastoe, Soft Matter, 2013, 9,
2365–2374.
79 P. Mirarefi and C. T. Lee, Biochim. Biophys. Acta, 2010,
1804, 106–114.
80 J. Zhang, S.-C. Wang and C. T. Lee, J. Phys. Chem. B, 2009,
113, 8569–8580.
81 K. Sakai, R. Yamazaki, Y. Imaizumi, T. Endo, H. Sakai and
M. Abe, Colloids Surf., A, 2012, 410, 119–124.
82 H. Sakai, S. Aikawa, W. Matsuda, T. Ohmori, Y. Fukukita,
Y. Tezuka, A. Matsumura, K. Torigoe, K. Tsuchiya,
K. Arimitsu, K. Sakamoto, K. Sakai and M. Abe, J. Colloid
Interface Sci., 2012, 376, 160–164.
83 I. Kim, J. F. Rabolt and P. Stroeve, Colloids Surf., A, 2000,
171, 167–174.
84 A. S. Malcolm, A. F. Dexter and A. P. J. Middelberg, Soft
Matter, 2006, 2, 1057–1066.
85 C. B. Minkenberg, L. Florusse, R. Eelkema, G. J. M. Koper
and J. H. van Esch, J. Am. Chem. Soc., 2009, 131,
11274–11275.
86 R. F. Tabor, D. D. Tan, S. S. Han, S. a Young, Z. L. E. Seeger,
M. J. Pottage, C. J. Garvey and B. L. Wilkinson, Chem. – Eur. J.,
2014, 20, 13881–13884.
87 F. Tu and D. Lee, J. Am. Chem. Soc., 2014, 136, 9999–10006.
88 J. Tang, M. F. X. Lee, W. Zhang, B. Zhao, R. M. Berry and
K. C. Tam, Biomacromolecules, 2014, 15, 3052–3060.
89 K. Fuhrmann, A. Po, C. Aeberli, B. Castagner and M. A.
Gauthier, ACS Nano, 2013, 9, 8243–8250.
90 M. Morikawa, K. Murata, K. Yamada and N. Kimizuka,
Chem. Lett., 2013, 42, 501–503.
91 X. Liu and N. L. Abbott, J. Colloid Interface Sci., 2009, 339,
1–18.
This journal is © The Royal Society of Chemistry 2016

Chem Soc Rev
92 J. Zhang, Y. Song, L. Cronin and T. Liu, J. Am. Chem. Soc.,
2008, 130, 14408–14409.
93 N. Aydogan and N. L. Abbott, Langmuir, 2001, 17, 5703–5706.
Published on 10 June 2016. Downloaded by INDIAN INSTITUTE OF TECHNOLOGY BOMBAY on 2/2/2022 11:49:32 AM.
94 T. Saji, K. Hoshino and S. Aoyagui, J. Am. Chem. Soc., 1985,
107, 6865–6868.
95 P. J. Middelberg, A. S. Malcolm and A. F. Dexter, Asia-Pac.
J. Chem. Eng., 2007, 2, 362–367.
96 A. F. Dexter and A. P. J. Middelberg, J. Phys. Chem. C, 2007,
111, 10484–10492.
97 E. A. Cornell, Handbook of Chemistry and Physics, CRC Press,
Boca Raton, Florida, 95th edn, 2014–2015.
98 J. J. Carroll, J. D. Slupsky and A. E. Mather, J. Phys. Chem.
Ref. Data, 1991, 20, 1201–1209.
99 X. Su, C. Fowler, C. O’Neill, J. Pinaud, E. Kowal, P. G. Jessop
and M. F. Cunningham, Macromol. Symp., 2013, 333,
93–101.
100 L. Wang, W. Qiao, C. Cao and Z. Li, Colloids Surf., A, 2008,
320, 271–274.
101 Q. Zhang, G. Yu, W.-J. Wang, B.-G. Li and S. Zhu, Macromol.
Rapid Commun., 2012, 33, 916–921.
102 C. O’Neill, C. Fowler, P. G. Jessop and M. F. Cunningham,
Green Mater., 2013, 1, 27–35.
103 W. Qiao, Z. Zheng and Q. Shi, J. Surfactants Deterg., 2012,
15, 533–539.
104 M. Chai, Z. Zheng, L. Bao and W. Qiao, J. Surfactants
Deterg., 2014, 17, 383–390.
105 Y. Ding, S. Chen, H. Xu, Z. Wang, X. Zhang, T. H. Ngo and
M. Smet, Langmuir, 2010, 26, 16667–16671.
106 Y. Zhao, K. Landfester and D. Crespy, Soft Matter, 2012, 8,
11687–11696.
107 X. Su, P. G. Jessop and M. F. Cunningham, Green Mater.,
2014, 2, 69–81.
108 Y. Qian, Q. Zhang, X. Qiu and S. Zhu, Green Chem., 2014,
16, 4963–4968.
109 J. Tang, P. J. Quinlan and K. C. Tam, Soft Matter, 2015, 11,
3512–3529.
110 W. Qiao, Z. Zheng and H. Peng, Eur. J. Lipid Sci. Technol.,
2011, 113, 841–847.
111 S. Salentinig, P. Jackson and A. Hawley, Macromolecules,
2015, 48, 2283–2289.
112 S. Dai, P. Ravi and K. C. Tam, Soft Matter, 2008, 4, 435–449.
113 B. Yan, D. Han, O. Boissière, P. Ayotte and Y. Zhao, Soft
Matter, 2013, 9, 2011–2016.
114 H. Liu, Z. Guo, S. He, H. Yin, C. Fei and Y. Feng, Polym.
Chem., 2014, 5, 4756–4763.
115 J. Guo, N. Wang, J. Wu, Q. Ye, C. Zhang, X.-H. Xing and
J. Yuan, J. Mater. Chem. B, 2014, 2, 437.
116 S. Kumar, X. Tong, Y. L. Dory, M. Lepage and Y. Zhao,
Chem. Commun., 2013, 49, 90–92.
117 H. Liu, Y. Zhao, C. A. Dreiss and Y. Feng, Soft Matter, 2014,
10, 6387–6391.
118 J. Zhang, D. Han, H. Zhang, M. Chaker, Y. Zhao and D. Ma,
Chem. Commun., 2012, 48, 11510–11512.
119 Q. Zhang and S. Zhu, ACS Macro Lett., 2014, 3, 743–746.
120 X. Su, M. F. Cunningham and P. G. Jessop, Polym. Chem.,
2014, 5, 940–944.
This journal is © The Royal Society of Chemistry 2016
View Article Online
Review Article
121 H. Lu, Z. Zhou, J. Jiang and Z. Huang, J. Appl. Polym. Sci.,
2015, 132, 41307–41314.
122 H. Che, M. Huo, L. Peng, T. Fang, N. Liu, L. Feng, Y. Wei
and J. Yuan, Angew. Chem., Int. Ed., 2015, 54, 8934–8938.
123 W. Wang, H. Liu, M. Mu, H. Yin and Y. Feng, Polym. Chem.,
2015, 6, 2900–2908.
124 H. Lu, J. Jiang, Z. Huang and S. Dai, J. Appl. Polym. Sci.,
2014, 131, 40872–40878.
125 B. Liu, H. Zhou, S. Zhou, H. Zhang, A. Feng, C. Jian, J. Hu,
W. Gao and J. Yuan, Macromolecules, 2014, 47, 2938–2946.
126 X. Wang, G. Jiang, Z. Wei, X. Li and B. Tang, Eur. Polym. J.,
2013, 49, 3165–3170.
127 P. Liu, Y. Zhang, W. J. Wang, B. G. Li and S. G. Zhu,
Materials, Green Mater., 2014, 2, 82–94.
128 A. R. Shirin-Abadi, A. Darabi, P. G. Jessop and M. F.
Cunningham, Polymer, 2015, 60, 1–8.
129 P. Schattling, I. Pollmann and P. Theato, React. Funct.
Polym., 2014, 75, 16–21.
130 C.-S. Chen, Y. Y. Lau, S. M. Mercer, T. Robert, J. H. Horton
and P. G. Jessop, ChemSusChem, 2013, 6, 132–140.
131 K. J. Boniface, R. R. Dykeman, A. Cormier, H.-B. Wang,
S. M. Mercer, G. Liu, M. F. Cunningham and P. G. Jessop,
Green Chem., 2016, 18, 208–213.
132 P. van de Wetering, E. E. Moret, N. M. Schuurmans-
Nieuwenbroek, M. J. van Steenbergen and W. E. Hennink,
Bioconjugate Chem., 1999, 10, 589–597.
133 A. Darabi, A. Rezaee Shirin-Abadi, P. G. Jessop and M. F.
Cunningham, Macromolecules, 2015, 48, 72–80.
134 P. G. Jessop, D. J. Heldebrant, X. Li, C. A. Eckert and C. L.
Liotta, Nature, 2005, 436, 93053.
135 L. Phan, D. Chiu, D. J. Heldebrant, H. Huttenhower,
E. John, X. Li, P. Pollet, R. Wang, C. a Eckert, C. L. Liotta
and P. G. Jessop, Ind. Eng. Chem. Res., 2008, 47, 539–545.
136 P. Styring and E. A. Quadrelli, Carbon dioxide utilisation:
closing the carbon cycle, Elsevier, Waltham, 2015.
137 T. Yamada, P. J. Lukac, M. George and R. G. Weiss, Chem.
Mater., 2007, 19, 967–969.
138 T. Yamada, P. J. Lukac, T. Yu and R. G. Weiss, Chem.
Mater., 2007, 19, 4761–4768.
139 T. Yu, T. Yamada, G. C. Gaviola and R. G. Weiss, Chem.
Mater., 2008, 20, 5337–5344.
140 L. Phan, J. R. Andreatta, L. K. Horvey, C. F. Edie, A. L. Luco,
A. Mirchandani, D. J. Darensbourg and P. G. Jessop, J. Org.
Chem., 2008, 73, 127–132.
141 D. J. Heldebrant, P. K. Koech, M. T. C. Ang, C. Liang,
J. E. Rainbolt, C. R. Yonker and P. G. Jessop, Green Chem.,
2010, 12, 713–721.
142 C. Wang, H. Luo, D. Jiang, H. Li and S. Dai, Angew. Chem.,
Int. Ed., 2010, 49, 5978–5981.
143 P. Pollet, C. A. Eckertabc and C. L. Liotta, Chem. Sci., 2011,
2, 609–614.
144 L. Phan, H. Brown, J. White, A. Hodgson and P. G. Jessop,
Green Chem., 2009, 11, 53–59.
145 C. Samor, C. Torri, G. Samor, D. Fabbri, P. Galletti, F. Guerrini,
R. Pistocchi and E. Tagliavini, Bioresour. Technol., 2010, 101,
3274–3279.
Chem. Soc. Rev., 2016, 45, 4391--4436 | 4433

Review Article
146 J. P. Hallett, P. G. Jessop, C. A. Eckert and C. L. Liotta, ACS
Symp. Ser., 2007, 975, 198–211.
147 P. G. Jessop, L. Phan, A. Carrier, S. Robinson, C. J. Dürr and
Published on 10 June 2016. Downloaded by INDIAN INSTITUTE OF TECHNOLOGY BOMBAY on 2/2/2022 11:49:32 AM.
J. R. Harjani, Green Chem., 2010, 12, 809–814.
148 J. R. Vanderveen, L. Patiny, C. B. Cahlifoux, M. J. Jessop
and P. G. Jessop, Green Chem., 2015, 17, 5182–5188.
149 J. Durelle, J. R. Vanderveen, Y. Quan, C. B. Chalifoux,
J. E. Kostin and P. G. Jessop, Phys. Chem. Chem. Phys.,
2015, 17, 5308–5313.
150 P. G. Jessop, Aldrichimica Acta, 2015, 48, 18–21.
151 E. Yilmaz and M. Soylak, J. Anal. At. Spectrom., 2015, 30,
1629–1635.
152 G. Lasarte-Aragon, R. Lucena, S. Cardenas and M. Valcarcel,
J. Sep. Sci., 2015, 38, 990–995.
153 J. R. Vanderveen, J. Durelle and P. G. Jessop, Green Chem.,
2014, 16, 1187–1197.
154 D. Fu, S. Farag, J. Chaouki and P. G. Jessop, Bioresour.
Technol., 2014, 154, 101–108.
155 C. Samorı̀, L. Pezzolesi, D. L. Barreiro, P. Galletti, A. Pasteris
and E. Tagliavini, RSC Adv., 2014, 4, 5999–6008.
156 P. G. Jessop, L. Kozycz, Z. G. Rahami, D. Schoenmakers,
A. R. Boyd, D. Wechsler and A. M. Holland, Green Chem.,
2011, 13, 619–623.
157 Y. Kohno, H. Arai and H. Ohno, Chem. Commun., 2011, 47,
4772–4774.
158 V. Blasucci, C. Dilek, H. Huttenhower, E. John, V. Llopis-
Mestre, P. Pollet, C. A. Eckert and C. L. Liotta, Chem.
Commun., 2009, 116–118.
159 V. Blasucci, R. Hart, V. L. Mestre, D. J. Hahne, M. Burlager,
H. Huttenhower, B. J. R. Thio, P. Pollet, C. L. Liotta and
C. A. Eckert, Fuel, 2010, 89, 1315–1319.
160 R. Hart, P. Pollet, D. J. Hahne, E. John, V. Liopis-Mestre,
V. Blasucci, H. Huttenhower, W. Leitner, C. A. Eckert and
C. L. Liotta, Tetrahedron, 2010, 66, 1082–1090.
161 I. Anugwom, P. Mäki-Arvela, P. Virtanen, P. Damlin,
R. Sjöholm and J.-P. Mikkola, RSC Adv., 2011, 1, 452–457.
162 E. Privalova, M. Nurmi, M. S. Marañón, E. V. Murzina,
P. Mäki-Arvela, K. Eränen, D. Y. Murzin and J. P. Mikkola,
Sep. Purif. Technol., 2012, 97, 42–50.
163 S. Hardy and M. A. Liauw, Chem. Eng. J., 2013, 233,
292–296.
164 M. E. Donaldson, V. L. Mestre, D. Vinci, C. L. Liotta and
C. A. Eckert, Ind. Eng. Chem. Res., 2009, 48, 2542–2547.
165 A. L. Rohan, J. R. Swtzwer, K. M. Flack, R. J. Hart,
S. Sivawamy, E. J. Biddinger, M. Talreja, M. Verma,
S. Faltermeier, P. T. Neilsen, P. Pollet, G. F. Schuette and
C. A. Eckert, ChemSusChem, 2012, 5, 2181–2187.
166 A. Holland, D. Wechsler, A. Patal, B. M. Molloy, A. R. Boyd
and P. G. Jessop, Can. J. Chem., 2012, 90, 805–810.
167 M. S. Shannon and J. E. Bara, Sep. Sci. Technol., 2012, 47,
178–188.
168 X. Cao, H. Xie, Z. Wu, H. Shen and B. Jing, ChemCatChem,
2012, 4, 1272–1278.
169 I. Anugwom, P. Mäki-Arvela, P. Virtanen, S. Willför,
R. Sjöholm and J. P. Mikkola, Carbohydr. Polym., 2012, 87,
2005–2011.
4434 | Chem. Soc. Rev., 2016, 45, 4391--4436
View Article Online
Chem Soc Rev
170 F. Saliu and M. Orlandi, Anal. Bioanal. Chem., 2013, 405,
8677–8684.
171 C. Samorı̀, D. López Barreiro, R. Vet, L. Pezzolesi, D. W. F.
Brilman, P. Galletti and E. Tagliavini, Green Chem., 2013,
15, 353–356.
172 Y. Du, B. Schuur, C. Samorı̀, E. Tagliavini and D. W. F.
Brilman, Bioresour. Technol., 2013, 149, 253–260.
173 D. Xiong, Z. Li, H. Wang and J. Wang, Green Chem., 2013,
15, 1941–1948.
174 G. Lasarte-Aragonés, R. Lucena, S. Cárdenas and
M. Valcárcel, Talanta, 2015, 131, 645–649.
175 G. Lasarte-Aragonés, R. Lucena, S. Cárdenas and
M. Valcárcel, Sep. Sci., 2015, 38, 990–995.
176 Q. Zhang, N. S. Qztekin, J. Barrault, K. De Oliveira Vigier
and F. Jerome, ChemSumChem, 2013, 6, 593–596.
177 Y. Yang, H. Xie and E. Liu, Green Chem., 2014, 16, 3018–3023.
178 L. Peng, J. Zhang, Z. Xue, B. Han, X. Sang, C. Liu and
G. Yang, Nat. Commun., 2014, 5, 4465.
179 P. Domı́nguez de Marı́a, J. Chem. Technol. Biotechnol., 2014,
89, 11–18.
180 F. Saliu, M. Anzano and A. Franzetti, Anal. Bioanal. Chem.,
2015, 407, 1801–1806.
181 C. Samorı̀, M. Basaglia, S. Casella, L. Favaro, P. Galletti,
L. Giorgini, D. Marchi, L. Mazzocchetti, C. Torri and
E. Tagliavini, Green Chem., 2015, 17, 1047–1056.
182 A. R. Boyd, P. Champagne, P. J. McGinn, K. M. MacDougall,
J. E. Melanson and P. G. Jessop, Bioresour. Technol., 2012,
118, 628–632.
183 S. M. Mercer and P. G. Jessop, ChemSusChem, 2010, 3,
467–470.
184 P. G. Jessop, S. M. Mercer, R. S. Brown and T. Robert, Water
With Switchable Ionic Strength, EP2534106 A1, 2012.
185 R. S. Brown, T. J. Clark, P. G. Jessop, B. E. Mariampillai,
S. M. Mercer, R. Resendes, T. Robert and D. Wechsler,
Systems and methods for use of water with switchable ionic
strength, WO2012079175 A1, 2012.
186 G. Lestari, M. Abolhasani, D. Bennett, P. Chase, A. Gu and
E. Kumacheva, J. Am. Chem. Soc., 2014, 136, 11972–11979.
187 S. M. Mercer, T. Robert, D. V. Dixon and P. G. Jessop, Catal.
Sci. Technol., 2012, 2, 1315–1318.
188 S. M. Mercer, T. Robert, D. V. Dixon, C.-S. Chen,
Z. Ghoshouni, J. R. Harjani, S. Jahangiri, G. H. Peslherbe
and P. G. Jessop, Green Chem., 2012, 14, 832–839.
189 T. Robert, S. M. Mercer, T. J. Clark, B. E. Mariampillai,
P. Champagne, M. F. Cunningham and P. G. Jessop, Green
Chem., 2012, 14, 3053–3062.
190 P. A. Lovell and R. J. Young, Introduction to polymers, CRC
Press, 3rd edn, 2011.
191 J. M. Asua, Polymer Reaction Engineering, Blachwell Publishing
Ltd, 2007.
192 Q. Zhang, W. J. Wang, Y. Lu, B. G. Li and S. Zhu, Macro-
molecules, 2011, 44, 6539–6545.
193 P. Liu, W. Lu, W. J. Wang, B. G. Li and S. Zhu, Langmuir,
2014, 30, 10248–10255.
194 N. Che, S. Yang, H. Kang, R. Liu, Z. Li, Z. Liu, P. Li, X. Qu
and Y. Huang, Polym. Chem., 2014, 5, 7109–7120.
This journal is © The Royal Society of Chemistry 2016

Chem Soc Rev
195 W. A. Braunecker and K. Matyjaszewski, Prog. Polym. Sci.,
2007, 32, 93–146.
196 M. Szwarc, Nature, 1956, 178, 1168–1169.
Published on 10 June 2016. Downloaded by INDIAN INSTITUTE OF TECHNOLOGY BOMBAY on 2/2/2022 11:49:32 AM.
197 M. F. Cunningham, Prog. Polym. Sci., 2008, 33, 365–398.
198 P. B. Zetterlund, Y. Kagawa and M. Okubo, Chem. Rev.,
2008, 108, 3747–3794.
199 J. Qiu, B. Charleux and K. Matyjaszewski, Prog. Polym. Sci.,
2001, 26, 2083–2134.
200 J. M. Asua, Prog. Polym. Sci., 2002, 27, 1283–1346.
201 F. J. Schork, Y. Luo, W. Smulders, J. P. Russum, A. Butté
and K. Fontenot, Adv. Polym. Sci., 2005, 175, 129–255.
202 J. B. McLeary and B. Klumperman, Soft Matter, 2006, 2,
45–53.
203 K. Matyjaszewski and J. Xia, Chem. Rev., 2001, 101, 2921–2990.
204 K. Matyjaszewski, Macromolecules, 2012, 45, 4015–4039.
205 L. Zhang, J. Qian, Y. Fan, W. Feng, Z. Tao and H. Yang, RSC
Adv., 2015, 5, 62229–62234.
206 Q. Zhang and S. Zhu, Macromol. Rapid Commun., 2014, 35,
1692–1696.
207 Q. Yan and Y. Zhao, Angew. Chem., Int. Ed., 2013, 52,
9948–9951.
208 H. Lu, Y. Liu, J. Jiang and Z. Huang, J. Appl. Polym. Sci.,
2015, 132, 41468–41476.
209 H. Jiang, E. Wang and J. Wang, RSC Adv., 2015, 5,
35622–35630.
210 Handbook of RAFT polymerization, ed. C. Barner-Kowollik,
Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
211 Z. Guo, Y. Feng, Y. Wang, J. Wang, Y. Wu and Y. Zhang,
Chem. Commun., 2011, 47, 9348–9350.
212 Z. Guo, Y. Feng, S. He, M. Qu, H. Chen, H. Liu, Y. Wu and
Y. Wang, Adv. Mater., 2013, 25, 584–590.
213 H. Liu, W. Wang, H. Yin and Y. Feng, Langmuir, 2015, 31,
8756–8763.
214 X. Jiang, C. Feng, G. Lu and X. Huang, ACS Macro Lett.,
2014, 3, 1121–1125.
215 J. Hu, M. R. Whittaker, Y. Li, J. F. Quinn and T. P. Davis,
Polym. Chem., 2015, 6, 2407–2415.
216 X. Jiang, C. Feng, G. Lu and X. Huang, Polymer, 2015, 64,
268–276.
217 W. Yuan, J. Shen and H. Zou, RSC Adv., 2015, 5,
13145–13152.
218 H. Zou and W. Yuan, Polym. Chem., 2015, 6, 2457–2465.
219 D. H. Solomon, J. Polym. Sci., Part A: Polym. Chem., 2005,
43, 5748–5764.
220 M. K. Georges, R. P. N. Veregin, P. M. Kazmaier and
G. K. Hamer, Macromolecules, 1993, 26, 2987–2988.
221 D. Bertin, D. Gigmes, S. R. A. Marque and P. Tordo, Chem.
Soc. Rev., 2011, 40, 2189–2198.
222 K. Zhou, J. Li, Y. Lu, G. Zhang, Z. Xie and C. Wu, Macro-
molecules, 2009, 42, 7146–7154.
223 V. Bütün, N. C. Billingham and S. P. Armes, J. Am. Chem.
Soc., 1998, 11818–11819.
224 V. Bütün, S. Liu, J. V. M. Weaver, X. Bories-Azeau, Y. Cai
and S. P. Armes, React. Funct. Polym., 2006, 66, 157–165.
225 J.-W. Lee and R. Klajn, Chem. Commun., 2015, 51,
2036–2039.
This journal is © The Royal Society of Chemistry 2016
View Article Online
Review Article
226 N. Li, L. Thia and X. Wang, Chem. Commun., 2014, 50,
4003–4006.
227 H. J. Zhang, Y. Zhao and Q. Yan, ACS Macro Lett., 2014, 3,
472–476.
228 S. Chen, C. X. Guo, Q. Zhao and X. Lu, Chem. – Eur. J., 2014,
20, 14057–14062.
229 H. Che, M. Huo, L. Peng, Q. Ye, J. Guo, K. Wang, Y. Wei
and J. Yuan, Polym. Chem., 2015, 6, 2319–2326.
230 F. S. Mohammed, S. Wuttigul and C. L. Kitchens, Ind. Eng.
Chem. Res., 2011, 50, 8034–8041.
231 R. G. Gilbert, Emulsion polymerization: a mechanistic
approach, Academic Press, London, San Diego, 1995.
232 M. S. Lovell and P. A. El-Aasser, Emulsion polymerization
and emulsion polymers, Wiley, New York, 1997.
233 V. Fischer, K. Landfester and R. Muñoz-Espı́, ACS Macro
Lett., 2012, 1, 1371–1374.
234 J. Zhang and B. Han, Acc. Chem. Res., 2013, 46, 425–433.
235 P. Brown, M. J. Wasbrough, B. E. Gurkan and T. A. Hatton,
Langmuir, 2014, 30, 4267–4272.
236 C. Liang, Q. Liu and Z. Xu, ACS Appl. Mater. Interfaces,
2014, 6, 6898–6904.
237 M. Yue, Y. Hoshino, Y. Ohshiro, K. Imamura and Y. Miura,
Angew. Chem., Int. Ed., 2014, 53, 2654–2657.
238 T. Yu, K. Wakuda, D. L. Blair and R. G. Weiss, J. Phys.
Chem. C, 2009, 113, 11546–11553.
239 D. Nagai, A. Suzuki, Y. Maki and H. Takeno, Chem. Commun.,
2011, 47, 8856–8858.
240 C. Zhao, J. Zhang, G. Yuan and C. C. Han, RSC Adv., 2013,
3, 9645–9648.
241 L. Lei, Q. Zhang, S. Shi and S. Zhu, Langmuir, 2015, 31,
2196–2201.
242 Q. M. Zhang, A. Ahiabu, Y. Gao and M. J. Serpe, J. Mater.
Chem. C, 2015, 3, 495–498.
243 S. S. Satav, S. Bhat and S. Thayumanavan, Biomacromolecules,
2010, 11, 1735–1740.
244 Y. Chen, T. Zhao, B. Wang, D. Qiu and N. Ma, Langmuir,
2015, 31, 8138–8145.
245 Y. Mai and A. Eisenberg, Chem. Soc. Rev., 2012, 41,
5969–5985.
246 J. F. Gohy, Adv. Polym. Sci., 2005, 190, 65–136.
247 T. Smart, H. Lomas, M. Massignani, M. V Flores-merino,
L. R. Perez and G. Battaglia, Review Literature And Arts Of
The Americas, 2008, 3, 38–46.
248 G. Riess and C. Labbe, Macromol. Rapid Commun., 2004,
25, 401–435.
249 N. Hadjichristidis, M. Pitsikalis and H. Iatrou, Adv. Polym.
Sci., 2005, 189, 1–124.
250 G. Gaucher, M.-H. Dufresne, V. P. Sant, N. Kang,
D. Maysinger and J.-C. Leroux, J. Controlled Release, 2005,
109, 169–188.
251 L. Zhang and A. Eisenberg, Science, 1995, 268, 21–24.
252 D. E. Discher and A. Eisenberg, Science, 2002, 297, 967–973.
253 A. Blanazs, S. P. Armes and A. J. Ryan, Macromol. Rapid
Commun., 2009, 30, 267–277.
254 D. E. Discher and F. Ahmed, Annu. Rev. Biomed. Eng., 2006,
8, 323–341.
Chem. Soc. Rev., 2016, 45, 4391--4436 | 4435

Review Article
255 J. S. Lee and J. Feijen, J. Controlled Release, 2012, 161,
473–483.
256 H.-Y. Chang, Y.-J. Sheng and H.-K. Tsao, Soft Matter, 2014,
Published on 10 June 2016. Downloaded by INDIAN INSTITUTE OF TECHNOLOGY BOMBAY on 2/2/2022 11:49:32 AM.
10, 6373–6381.
257 R. P. Brinkhuis, F. P. J. T. Rutjes and J. C. M. van Hest,
Polym. Chem., 2011, 2, 1449–1462.
258 F. Meng, Z. Zhong and J. Feijen, Biomacromolecules, 2009,
10, 197–209.
259 M.-H. Li and P. Keller, Soft Matter, 2009, 5, 927–937.
260 W. Li, Y. Yang, T. Luo, J. Zhang and B. Han, Phys. Chem.
Chem. Phys., 2014, 16, 3640–3647.
261 Z. Zheng, C. Liu and W. Qiao, Eur. J. Lipid Sci. Technol.,
2015, 117, 1673–1678.
262 M. E. Boot-Handford, J. C. Abanades, E. J. Anthony,
M. J. Blunt, S. Brandani, N. Mac Dowell, J. R. Fernandez,
M.-C. M.-C. Ferrari, R. Gross, J. P. Hallett, R. S. Haszeldine,
P. Heptonstall, A. Lyngfelt, Z. Makuch, E. Mangano,
R. T. J. Porter, M. Pourkashanian, G. T. Rochelle, N. Shah,
J. G. Yao, P. S. Fennell, J. R. Fernández, M.-C. M.-C. Ferrari,
R. Gross, J. P. Hallett, R. S. Haszeldine, P. Heptonstall,
A. Lyngfelt, Z. Makuch, E. Mangano, R. T. J. Porter,
M. Pourkashanian, G. T. Rochelle, N. Shah, J. G. Yao and
P. S. Fennell, Energy Environ. Sci., 2014, 7, 130–189.
263 D. M. D’Alessandro, B. Smit and J. R. Long, Angew. Chem.,
Int. Ed., 2010, 49, 6058–6082.
264 H. Xie, X. Yu, Y. Yang and Z. K. Zhao, Green Chem., 2014,
16, 2422–2427.
265 H. Zhou, W.-Z. Zhang, Y.-M. Wang, J.-P. Qu and X.-B. Lu,
Macromolecules, 2009, 42, 5419–5421.
4436 | Chem. Soc. Rev., 2016, 45, 4391--4436
View Article Online
Chem Soc Rev
266 Y. Furusho and T. Endo, J. Polym. Sci., Part A: Polym. Chem.,
2013, 51, 3404–3411.
267 J. Kainz, P. David, L. Werz, C. Troll and B. Rieger, RSC Adv.,
2015, 5, 9556–9560.
268 Y. Wang, Y. Shang, X. Li, T. Tian, L. Gao and L. Jiang,
Polymers, 2014, 6, 1403–1413.
269 X. Su, M. F. Cunningham and P. G. Jessop, Chem. Commun.,
2013, 49, 2655–2657.
270 Y. Zhang, Y. Han, Z. Chu, S. He, J. Zhang and Y. Feng,
J. Colloid Interface Sci., 2013, 394, 319–328.
271 H. Lu, Z. Huang, L. L. Yang and S. Dai, J. Dispersion Sci.
Technol., 2014, 36, 252–258.
272 L. Guo, R. Zhang, X. Zhao, H. Gan, B. Song, J. Chen,
W. Zhu, L. Hua and Z. Hou, J. Porous Mater., 2014, 21,
739–746.
273 Y. Zhang, P. An, X. Liu, Y. Fang and X. Hu, Colloid Polym.
Sci., 2014, 293, 357–367.
274 V. Stastny and D. M. Rudkevich, J. Am. Chem. Soc., 2007,
129, 1018–1019.
275 D. Y. Hegh, S. M. Mackay and E. W. Tan, RSC Adv., 2014, 4,
31771–31774.
276 K. Tanaka, K. Yamamoto and J. I. Kadokawa, Carbohydr.
Res., 2014, 398, 25–30.
277 H.-D. Wang, P. Jessop, J. Bouchard, P. Champagne and
M. Cunningham, Cellulose, 2015, 22, 3105–3116.
278 H. B. Jung, K. C. Carroll, S. Kabilan, D. J. Heldebrant,
D. Hoyt, L. Zhong, T. Varga, S. Stephens, L. Adams,
A. Bonneville, A. Kuprat and C. A. Fernandez, Green Chem.,
2015, 17, 2799–2812.
This journal is © The Royal Society of Chemistry 2016