CHAPTER FOUR

Progress in Polymer Nanoreactors:

Spherical Polyelectrolyte Brushes
Ayyaz Ahmad, Xiaochi Liu, Li Li, Xuhong Guo
State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai,
P.R. China

Contents
1. Introduction 194
2. Synthesis of SPB 196
2.1 Photoemulsion polymerization 196
2.2 Thermocontrolled emulsion polymerization 196
2.3 Direct grafting on poly(butadiene) core 197
2.4 Controlled radical polymerization: ATRP and RAFT 199
3. Functionalization of SPB 201
3.1 Stimuli-responsive brushes 201
3.2 Organic–inorganic hybrid SPB 207
4. Applications of SPB as Nanoreactors 207
4.1 Donnan effect and counterion distribution 208
4.2 As ideal nanoreactors 209
4.3 In catalysis 215
4.4 In protein immobilization 217
5. Conclusion 218
References 219

Abstract
The distinctive features of spherical polyelectrolyte brushes (SPB) as ideal nanoreactors
are discussed. SPB containing colloidal particles on which polyelectrolyte chains have
been densely grafted offer a wide range of potential applications. They are ideally suited
for the generation and immobilization of metal or metal oxide nanoparticles, which can
be applied as smart catalysts in chemical industry. SPB can also be used for immobili-
zation of proteins and enzymes. The response to external stimuli makes SPB unique in
the field of nanoreactors.

Advances in Chemical Engineering, Volume 44 # 2014 Elsevier Inc. 193

ISSN 0065-2377 All rights reserved.
http://dx.doi.org/10.1016/B978-0-12-419974-3.00004-X
194 Ayyaz Ahmad et al.

1. INTRODUCTION
In the past two decades, research in polymer brushes has received
much consideration due to their diverse and distinct applications in different
fields like protein immobilization (Efremova et al., 2001), drug delivery
(Cheng et al., 2008), film coating (Mei et al., 2006; Roosjen et al.,
2006), catalyst (Lu et al., 2007a), and nanoreactors (Ohno et al., 2003;
Santer and Ruhe, 2004). They consist of polymeric chains densely attached
or restricted by one end to a surface or an interface. These chains are
stretched on the surface in a dense pattern, forming a brushlike structure
(Milner, 1991). When polyelectrolyte (PE) chains are tethered to the host
surface, PE brushes are formed. The confinement of counterions within
the PE brushes makes them very special. When polymer chains carrying
charges are brought into contact with a surface, the structural and the phys-
ical properties of the brushes are determined by electrostatic interaction
(Pincus, 1991; Zhou and Huck, 2006). The charge and charge density of
the polymer control its interaction with the substrate (Fleer et al., 1995).
The tethering of these PE brushes can be done by two ways: physical adsorp-
tion (Van de Steeg et al., 1992) and chemical grafting or covalent attachment
(Milner, 1991). PE brushes can be attached to a planar surface, cylinder
(Belder et al., 1997), or sphere (Muller et al., 2000).
Spherical polyelectrolyte brushes (SPB) consist of a spherical core of
polymeric material, where linear PE chains are attached either by covalent
bond or by physical adsorption (Ballauff, 2007; Blencowe et al., 2009; Xu
et al., 2010a). A schematic diagram is shown in Fig. 4.1.
SPB have great advantages over the planar brush. Hariharan et al. (1998)
have concluded that the sensitivity of the PE brush thickness to pH or ionic
strength is greatly affected by the curvature. Counterions are confined in the
PE shells of SPB, rendering it more productive.
Theoretical approaches to SPB have been discussed in a number of
papers (Hanske et al., 2012a,b; Zhulina and Borisov, 1996; Zhulina and
Rubinstein, 2012; Zhulina et al., 1995, 1999, 2000). Depending on the
external salt concentration, SPB can be distinguished into three main
regimes: the neutral brush regime (with very high salt concentration), the
salted brush regime (with moderate salt concentration and comparable ionic
strengths inside and outside the SPB), and the osmotic brush regime (with
very low salt concentration). The counterion distribution in SPB is a func-
tion of the distance from the grafting surface.
Progress in Polymer Nanoreactors 195

Figure 4.1 Schematic diagram of SPB (Wu et al., 2012a).

SPB are mainly prepared by surface-initiated polymerization techniques

with improved control of surface coverage, thickness and composition over
dendrimers (highly branched macromolecules) or star polymers. They are
more stable than directly assembled polymer structures, such as vesicles
(polymersomes) and micelles prepared from amphiphilic block copolymers
(Cabane et al., 2012).
Two major grafting methods are used: “grafting to” and “grafting from.”
In the former method, presynthesized PE chains are attached to a suitable
substrate. Grafting density is limited by the difficulty of diffusing large PE
chains to the substrate and attaching onto the surface (Baum and Brittain,
2002). The “grafting from” technique, a surface-initiated process, offers
diverse advantages over the “grafting to” approach. The “grafting from”
technique uses an initiator that is covalently bound to the surface, forming
polymers tethered to the substrate. Since the diffusion of small monomer
molecules is much easier than their polymer, the “grafting from” technique
can result in higher grafting density than the “grafting to” method (Hertler
et al., 1990).
In this review, the synthesis, functionalization, and applications of SPB
will be summarized. The effectiveness and characteristics of SPB with
196 Ayyaz Ahmad et al.

colloidal cores and PE brushes as ideal nanoreactors will be demonstrated

(Sharma and Ballauff, 2004). The assembly of PE chains in SPB makes them
more versatile as nanoreactors. For example, counterions confined in SPB
layers can be replaced by metal or metal complex ions and reduced or oxi-
dized to yield nanosized metal or metal oxide particles (Schrinner
et al., 2007).

2. SYNTHESIS OF SPB
Since chemically grafted SPB show greater stability and controllable
grafting density, this method of preparation has become more popular than
physical adsorption. Chemical methods include photoemulsion polymeriza-
tion, thermocontrolled emulsion polymerization, atom transfer radical poly-
merization (ATRP), and reversible addition-fragmentation chain
transfer (RAFT).

2.1. Photoemulsion polymerization

The photoemulsion polymerization method was first employed by (Guo et al.,
1999) to synthesize SPB. This method is divided into three steps (Fig. 4.2). First,
spherical polystyrene (PS) cores with narrow size distribution are prepared
through conventional polymerization. Second, a thin layer of photoinitiator
2-[p-(2-hydroxy-2-methylpropiophenone)]-ethylene glycol-methacrylate
(HMEM) is grafted on the core using a controlled emulsion polymerization
technique. Third, PE chains are grown on the core surface through polymer-
ization of monomers dissolved in water under UV irradiation (Gliemann et al.,
2006; Guo and Ballauff, 2000; Yuan et al., 2012). A schematic representation is
shown in Fig. 4.2.
Photoemulsion polymerization allows for control of the contour length
of tethering chains by changing monomer concentrations, and of grafting
density by changing photoinitiator doses. Since grafted PE chains can be
cleaved from the remaining ester bond in HMEM by a strong base, all per-
tinent parameters of SPB, including contour length, grafting density and
size, can be measured accurately (de Robillard et al., 2000).

2.2. Thermocontrolled emulsion polymerization

Thermocontrolled emulsion polymerization has offered a new way to syn-
thesize SPB. This method has some advantages over photoemulsion poly-
merization. For example, it is easy to scale up, and the polymerization
Progress in Polymer Nanoreactors 197

PS PS PS

Step 1: PS– Step 2

core latex Shell
Photoinitiator
HMEM
Step 3
Shell composed of
linear polyelectrolyte
chains

B O
O O C OH
C O
HMEM

O
O O C + C OH
C O

Figure 4.2 (A) Schematic representation of SPB preparation by photoemulsion poly-

merization; (B) decomposition of HMEM.

can be triggered by controlling the temperature. In this method, the core

latex is prepared by redox emulsion polymerization, then a thin layer of
thermocontrolled initiator is applied to the core (Wang et al., 2010). The
synthesis of the thermoinitiator is shown in Fig. 4.3.
A thermocontrolled initiator is grafted on the core, and SPB are grafted
on the core using the “grafting from” technique at controlled temperature
(Wang et al., 2011).

2.3. Direct grafting on poly(butadiene) core

Special initiators with end C]C double bonds are normally required for the
grafting of PE chains on the core by radical copolymerization (Guo
et al., 1999).
198 Ayyaz Ahmad et al.

O CH3 CH3O
Cat.
AIBN + 2HO—CH2CH2–OH HO CH2CH2 O C C N=N C C O CH2CH2 OH
CH3 CH3

O CH3 CH3O O
HO CH2CH2 O C C N=N C C O CH2CH2 OH + 2CH2= C C Cl
CH3 CH3 CH3

CH3 O CH3 CH3O CH3

H2C C C O (CH2)2 O C C N N C C O (CH2)2 O C C CH2
O CH3 CH3 O

Figure 4.3 Synthesis of thermoinitiator BPAB (Wang et al., 2010).

Figure 4.4 PAA brushes on PB core by (A) direct thermoinitiated emulsion polymeriza-
tion, and (B) photoemulsion polymerization (Li et al., 2012).

However, Li et al. (2012) prepared SPB on industrial poly(butadiene)

(PB) latex particles, whose abundant residual C]C double bonds allow
for grafting brushes through radical polymerization with a common initiator
instead of the special initiators. In comparison, photoemulsion polymeriza-
tion was also employed to prepare SPB on the PB core. The schematic dia-
gram of these two processes is given in Fig. 4.4.
Progress in Polymer Nanoreactors 199

2.4. Controlled radical polymerization: ATRP and RAFT

ATRP as a living free radical polymerization method to prepare SPB has
been reported to have advantages over conventional free radical polymeri-
zation. ATRP depends on the reversible redox activation of a dormant alkyl
halide-terminated polymer chain end by a halogen transfer to a transition
metal complex. The formal homolytic cleavage of the carbon–halogen
bond, which falls out, yields a free and active carbon-centered radical species
at the polymer chain end. This activation step depends on a single electron
transfer from the transition metal complex to the halogen atom, which
guides the oxidation of the transition metal complex. Then the oxidized
form of the catalyst reconverts the dispersing radical chain end to the
corresponding halogen-capped dormant species. Many parameters, such
as the ligand–transition metal ratio, Cu(II)–Cu(I) ratio, type of ligand, coun-
terion, solvent, or initiator, manipulate the performance of ATRP, and thus
present the possibility of fine-tuning the polymerization (Barbey et al., 2009;
Coessens et al., 2001; Polzer et al., 2011; Wang and Matyjaszewski, 1995;
Zhang et al., 2013). This method provides better control over the molecular
weight and distribution of PE chains (Coessens et al., 2001). The synthesis of
SPB via ATRP is shown schematically in Fig. 4.5 (Polzer et al., 2011).
The RAFT method is another technique for designing complex macro-
molecular structures with a wide range of choices for monomers (Lowe
et al., 2003). The mechanism of RAFT polymerization is given in
Fig. 4.6 (Smith et al., 2010).
In RAFT polymerization, the original radicals were commonly generated
by traditional methods like azo- or photoinitiators as well as gamma radiation
(Quinn et al., 2002). A propagating oligomeric chain is formed when the initial
radical reacted with the monomer. The main component in RAFT

Figure 4.5 Schematic diagram of SPB via ATRP (Polzer et al., 2011).
200 Ayyaz Ahmad et al.

Initiation
kd •
Initiator 2I
•
I + Monomer Pn•
Pre-equilibrium
kadd • kb •
Pn• + S C S R Pn S C S R Pn S C S + R
k–add k–b
Z Z Z
Reinitiation
•
R• + Monomer Pm
Main Equilibrium
kadd • k–add
Pm• + S C S Pn Pm S C S Pn Pm S C S + Pn•
k–add kadd
Z Z Z

Monomer Monomer
Termination

• • • kt1
I ,, R , Pn Pm• Dead polymer
Figure 4.6 RAFT polymerization mechanism (Smith et al., 2010).

polymerization is chain transfer agents (CTA), which are usually

thiocarbonylthio compounds. In the pre-equilibrium step, the propagating
chain reacts with CTA and forms an intermediate radical. This reaction is
reversible. The main equilibrium step involves the degenerative transfer of
the thiocarbonylthio end group between propagating chains, through the for-
mation and fragmentation of an intermediate radical. The monomer is often
consumed during the main equilibrium and the number of monomer additions
can vary depending on reaction conditions (Boyer et al., 2010; Smith
et al., 2010).
RAFT polymerization is suited to aqueous solutions and emulsion poly-
merization, and thus has been widely used to prepare SPB (Bernadette et al.,
2010; Edmondson et al., 2004; McCormick et al., 2006). The core–shell
structure of amphiphilic block copolymers via RAFT-mediated polymeri-
zation is given in Fig. 4.7 (Liu et al., 2011).
In ATRP, the activator is sensitive to oxygen, which necessitates thor-
ough removal of oxygen prior to polymerization and use of equimolar
amounts of initiators (alkyl halide) and mediators (Wang and
Matyjaszewski, 1995). In RAFT polymerization, polymer architecture with
predictable molecular weight and narrow molecular weight distribution can
be produced. Synthesis of RAFT agents is very costly, however, and requires
multistep reactions (Perrier et al., 2005). For in-depth information regarding
Progress in Polymer Nanoreactors 201

Figure 4.7 SPB prepared by RAFT polymerization (Liu et al., 2011).

RAFT and ATRP polymerization, please see recent reviews

(Matyjaszewski, 2012; Matyjaszewski and Xia, 2001; Moad et al., 2008a,b).

3. FUNCTIONALIZATION OF SPB
3.1. Stimuli-responsive brushes
Stimuli-responsive polymer brushes can exhibit changes in conformation,
surface energy, or charge state, in response to external stimuli such as
changes in solvent, temperature, pH, ionic strength, light, or mechanical
stress. The discovery of controllable and reversible polymer chain conforma-
tion and surface energy has offered exciting and novel possibilities for the
fabrication of adaptive or responsive surfaces and interfaces (Ahn et al.,
2008; Luzinov et al., 2008; Minko, 2006; Pasparakis and Vamvakaki,
2011). Details of different responsive brushes are given below.

3.1.1 Response to pH and ionic strength

A variation in pH changes the ionization state that accompanies conforma-
tional changes in the brushes. Through pH and ionic strength, the brush can
be switched on or off, which can be used for catalysis or protein immobi-
lization. All PEs responsive to ionic strength and weak PEs responsive to pH
are well known. The pH-responsive polymers contain acidic (e.g., carboxyl)
or basic (e.g., amino) groups that are capable of releasing or accepting pro-
tons, and their degree of dissociation depend on the pH (Binks et al., 2007).
The size and counterion distribution of SPB consisting of weak PE chains
are thus sensitive to pH and ionic strength. Poly(acrylic acid) (PAA) brushes
are well-known pH- and ionic strength-responsive SPB (Fig. 4.8) (Guo and
Ballauff, 2001). At low pH, PAA chains are nearly uncharged and form a
crowded layer (Guo and Ballauff, 2000, 2001). At high pH, completely
202 Ayyaz Ahmad et al.

200
L (nm)

100

0
0 2 4 6 8 10 12 14
pH
Figure 4.8 Thickness of PAA SPB as a function of pH. The changing parameter is ionic
strength, by using different concentrations of KCl. Symbols denote: crosses, 1 M; open
squares, 0.1 M; triangles, 0.01 M, open circles, 0.001 M, filled squares, 0.0001 M (Guo and
Ballauff, 2001).

charged chains stretch out to almost full length if the solution has low salt
concentration (Marra et al., 2003). Due to their response toward pH,
PAA SPB can adsorb proteins at low pH and release protein molecules at
high pH (Wittemann and Ballauff, 2004; Wittemann et al., 2003a,b).
Polystyrene sulfonate (PSS) brushes respond to ionic strength but not to
pH (Guo and Ballauff, 2001). In aqueous suspension, sulfonate groups are
completely dissociated, independent of pH. The negative charge in the shell
layer results in electrostatic repulsion of PSS chains and a strong imprison-
ment of sodium ions in the shell layer. As a result, PE chains are linearly pro-
longed as long as the electrolyte concentration in suspension is low. When
NaCl is added to the SPB suspension, the osmotic pressure difference
between the shell and the solvent decreases and the effective negative charge
of PE brushes is screened. This results in a contraction of the PSS chains, and
in shrinkage of the shell layer (Schuerer et al., 2011).
Tsyalkovsky et al. synthesized binary polymeric brushes of poly(2-
vinylpyridine) (P2VP) and poly(ethylene glycol) (PEG), in which P2VP is
the pH-sensitive component. The P2VP part of the brush has shown significant
variations in swelling as a function of pH. At low pH, the grafted P2VP chains are
protonated and extended (Tsyalkovsky et al., 2010). This is shown in Fig. 4.9.
Progress in Polymer Nanoreactors 203

Figure 4.9 pH-responsive brushes of P2VP on silica nanoparticles (Tsyalkovsky et al., 2010).

3.1.2 Response to magnetic field

Magnetic nanoparticles (NPs) have been used in many advanced technolog-
ical areas, including biology, pharmacy, and diagnostics (Dyal et al., 2003).
When magnetic NPs are introduced into SPB, they respond to external
magnetic fields accordingly, which should be very useful for SPB recovery
and controlled drug delivery (Lattuada and Hatton, 2006).
Xu et al. prepared superparamagnetic magnetite NPs with an average
diameter of 10 nm, enclosed in the brush core. The hybrid brushes become
superparamagnetic. This system can be responsive to relatively weak mag-
netic fields (40 and 300 mT) (Xu et al., 2010b). Another magnetic-
responsive SPB has been prepared via ATRP, through the layer-by-layer
method, with a core of SiO2 and a shell of magnetic (Fe3O4) NPs and
poly(sodium 4-styrenesulphonate) (Lei et al., 2007). Due to the magnetic
response, SPB can be recycled or separated by employing an external mag-
netic field after use (Fig. 4.10) (Kaimin et al., 2010). When magnetic
response was embedded in the core–shell architecture of SPB, the capability
of other responses was enhanced (Chen et al., 2011; Louguet et al., 2012).
Chen et al. (2011) showed that PAA SPB with magnetic NPs inside the core
are sensitive to both pH value and ionic strength.
Ultrafine nanosized magnetic particles can be prepared in situ by using
SPB as a nanoreactor (Zhu et al., 2012). Magnetic response is thus induced
in SPB. The applications of Magnetic spherical polyelectrolyte brushes
(MSPB), in addition to separation and recycling, include heat generation
(Gelbrich et al., 2010).

3.1.3 Response to temperature

Thermoresponsive brushes allow for adjustment of catalytic activity within
a nanoreactor system through changing thermodynamic conditions. In such
a system, immobilized metal NPs or proteins have access to the outer
204 Ayyaz Ahmad et al.

1000

DH (nm)

100 Magnet

Shake

10
1 2 3 4 5 6
Redispersion cycles
Figure 4.10 Recycling of SPB with magnetic response (Kaimin et al., 2010).

environment at certain temperature ranges, allowing the SPB “nanoreactors”

to be turned on or off by temperature. SPB containing poly(-
N-isopropylacrylamide) (PNIPAm) chains show temperature responses. If a
polymer undergoes a phase transition from a soluble state to an insoluble state
above the critical temperature, it is characterized as having a lower critical solu-
tion temperature (LCST), and conversely an upper critical solution tempera-
ture (Karg et al., 2011; Wang et al., 2011). Figure 4.11 shows the change in
size of PNIPAm brushes upon changing the temperature across the LCST.
The hydrophobic modification or copolymerization of PNIPAm
with other monomers may have an impact on the LCST. The
incorporation of a hydrophilic monomer (e.g., acrylic acid, sodium
acrylate, acrylamide, N-methyl-N-vinylacetamide, N-vinylacetamide,
or N-vinyl-2-pyrrolidinone) increases the thermal phase transition tem-
perature (Lin et al., 2006; Xue and Hamley, 2002), while the reverse is
true when hydrophobic monomers (e.g., di-n-propylacrylamide,
di-noctylacrylamide or di-dodecylacrylamide) are used (Xue and
Hamley, 2002). The effect of molecular weight on LCST is more
significant for a low molecular weight system. The LCST for
PNIPAm copolymer were 21.7, 24.8, 26.5, and 29.3
C with the num-
ber average molecular weight of 3000, 3400, 4200, and 5000 g/mol,
respectively (Duan et al., 2006). Ranganathan et al. (2008) utilized
the temperature-sensitive properties of PNIPAm to generate reversible
Progress in Polymer Nanoreactors 205

Figure 4.11 PNIPAm response to temperature (Lu and Ballauff, 2011).

nanoaggregates (core–shell structure) above the LCST of PNIPAm by

controlling the composition and molecular weight of the PNIPAm core
and poly(N,N dimethylacrylamide) PDMA corona.
PEG or PEO is a water-soluble polymer that possesses a LCST greater
than 90
C (Dai et al., 2009). SPB formed by a copolymer poly-
(ethylene oxide)-graft-poly(N,N-dimethylaminoethylmethacrylate) (PEO-g-
PDMAEMA) are also sensitive to temperature (Sui et al., 2011).

3.1.4 Multiresponsive SPB

In recent years, research in multiresponsive SPB has increased dramatically
(Lee et al., 2010; Pasparakis and Vamvakaki, 2011; Peng and Bhushan, 2012;
Sui et al., 2011). These brushes respond to changes in more than one param-
eter and can be used to trigger the “catch and release” of nanomaterials in
response to more than one parameter. Figure 4.12 shows the schematic dia-
gram of SPB consisting of thermoresponsive PNIPAm and pH-responsive
PAA (Huang et al., 2012a; Wang et al., 2011). As shown in Fig. 4.13,
the brush thickness as determined by DLS was affected by both temperature
and pH.
Another example of multiresponsive brushes shows response to magnetic
fields and pH (Yu et al., 2013). Imidazole group-modified PEG-
polypeptides were grafted onto silica-coated Fe3O4 NPs. The Fe3O4
responded to external magnetic fields while the polymeric shell responded
to pH. SPB assembled by PEO-g-PDMAEMA, a copolymer synthesized by
ATRP, responded to shear, ionic strength, and pH (Fig. 4.14) (Sui
et al., 2011).
206 Ayyaz Ahmad et al.

Figure 4.12 Schematic diagram of multiresponsive SPB (Huang et al., 2012a).

A B
140 140
pH = 12
120 120
Brush layer thickness (nm)

Brush layer thickness (nm)

100 100

80 80
15 °C
PNIPAM
60 60
PAA
pH = 2
40 40

20 PNIPAM
50 °C 20
PAA
0 0
0 2 4 6 8 10 12 14 10 20 30 40 50
pH Temperature (°C)
Figure 4.13 Change in brush thickness as a function of pH (A) and Temperature (B)
(Wang et al., 2011).

Concentrated solutions Low shear High shear

pH/thermo thickening Shear thickening

Dilute solutions
self-assembly

Poly(EO-co-Gly)
200 nm 2 mm
PDMAEMA
pH = 8 NaCI = 5 wt%

Figure 4.14 Schematic diagram of shear-, ionic strength-, and pH-responsive (PEO-g-
PDMAEMA) (Sui et al., 2011).
Progress in Polymer Nanoreactors 207

20

15

Zeta potential (mV) 10

−5

−10

−15

−20
4 6 8 10 12 14
pH
Figure 4.15 Zeta potential of HA with grafted PS-co-4-VP. Symbols denote: in (-□-) pH is
increased from 3 to 13.5; in (-▪-) pH is decreased from 13.5 to 3 (Li et al., 2011).

3.2. Organic–inorganic hybrid SPB

Due to their versatile applications, organic–inorganic hybrid SPB have
attracted great attention (Daigle and Claverie, 2008; Karg et al., 2011; Lei
and Bi, 2007; Pyun and Matyjaszewski, 2001; Sun et al., 2007; Tchoul
et al., 2012; Wei et al., 2008). For example, for SPB formed by
polystyrene-co-4-vinylpyridine grafted on hydroxyapatite (HA) particles
(Li et al., 2011), the pH response can be characterized by zeta potential ver-
sus pH (Fig. 4.15).
Magnetic NPs exhibit stability when NaPSS has been grafted onto the sur-
face to form a core–shell structure (Bakandritsos et al., 2008). Organic–
inorganic hybrid SPB with grafted poly(sodium-p-styrenesulfonate) on mod-
ified SiO2 particles have been reported (Fig. 4.16) (Su et al., 2012).
Huang et al. (2012b) have prepared hollow organic–inorganic NPs based
on PAA SPB. Figure 4.17 shows the SEM images of hollow silica NPs,
which should be an ideal candidate for drug delivery.

4. APPLICATIONS OF SPB AS NANOREACTORS

SPB have been applied in numerous fields due to their different char-
acteristics. In the following section, their vast applications as nanoreactors are
discussed.
208 Ayyaz Ahmad et al.

Rh

SiO2
Rc

SO3−

Figure 4.16 Organic–inorganic SPB (Su et al., 2012).

Figure 4.17 SEM image of hollow silica nanoparticles (Huang et al., 2012b).

4.1. Donnan effect and counterion distribution

The Donnan effect in PE brushes has diverse technological and biophysical
applications (Ruhe et al., 2004). It is also commonly encountered in systems
where ion concentration gradients are maintained across the systems (Das
et al., 2002). Donnan effect has therefore been the subject of numerous
theoretical studies aimed at predicting properties such as the electro-
chemical potential and osmotic pressure of salt-free suspensions of SPB
Progress in Polymer Nanoreactors 209

(Blencowe et al., 2009). Measurements of the osmotic pressure of quenched

systems directly confront counterion activity around SPB and permit for a
complete test of the theory (Das et al., 2002).

4.2. As ideal nanoreactors

NPs are normally synthesized by reduction of metal ions in the presence of a
stabilizer (Beaucage et al., 1999; Garcia et al., 2003; Lenggoro et al., 2000;
Lu and Chen, 2000; Ma et al., 2002; Sayo et al., 1999; Schildenberger et al.,
2000; Schnaiter et al., 1999; Tan et al., 1999; Wang et al., 2002; Zhou et al.,
2002). Due to confinement of counterions within brushes, SPB have proven
to be a well-defined and effective nanoreactor. Metal ions replace the coun-
terions confined within SPB, and NPs are created by the reduction of metal
ions. NPs are stable in SPB without adding stabilizer.
Sharma and Ballauff (2004) have generated gold (Au) NPs in SPB. They
generated Au NPs on cationic SPB containing poly(aminoethyl methacry-
late hydrochloride) (PAEMH) brushes. Chloride ions are confined as coun-
terions between brushes, which were exchanged against AuCl4  ions. Then
they were reduced to gold NPs on the SPB surface. A schematic diagram is
shown in Fig. 4.18.
The size of gold NPs of gold can vary. SAXS analysis revealed that Au
crystalline particles are in the range of 2–3 nm while amorphous Au particles
are 1.3 nm (Schrinner et al., 2007).
Platinum NPs were prepared in the same manner in an SPB nanoreactor
(Mei et al., 2005), using poly((2-methylpropenoyloxyethyl)
trimethylammonium chloride) as the cationic SPB. H2PtCl6 was utilized
as a precursor for Pt NPs. The TEM image shows that the size of Pt NPs
is around 1.9–2.1 nm (Fig. 4.19).
Lu et al. (2007b) have synthesized silver (Ag) NPs in an SPB nanoreactor
in a different way. The PS core was synthesized and HMEM applied as
photoinitiator as described by previous literature (Guo et al., 1999; Marra
et al., 2003; Mei et al., 2003). In the final step, silver acrylate was used as
a functional monomer to grow SPB on the PS core. Meanwhile, Ag NPs
were generated from Agþ, which were confined as counterions in the pres-
ence of UV light (Fig. 4.20).
Our group has currently synthesized size-controlled silver (Ag) NPs in
SPB. To increase the particle size of Ag, equal amounts of Ag precursor were
added and the reduction reaction was repeated. The amount of Ag NPs was
determined by TGA (Fig. 4.21).
210 Ayyaz Ahmad et al.

Figure 4.18 In this representation, I, II have exchanged counterions with HAuCl4 to give
III, which was then reduced by NaBH4 to generate the gold NPs shown in IV (Sharma and
Ballauff, 2004).

Figure 4.19 TEM image showing the size of Pt NPs generated by SPB nanoreactor (Mei
et al., 2005).
Progress in Polymer Nanoreactors 211

Figure 4.20 Schematic procedure for generation of Ag NPs on SPB (Lu et al., 2007b).

Figure 4.21 Amount of Ag nanoparticles after each generation cycle as determined by

TGA.

Recently, our group has introduced a unique method to synthesize SPB

containing magnetite NPs (MSPB) (Kaimin et al., 2010). A controlled and
recycleable SPB is prepared by introducing magnetism through external
stimuli such as a magnetic field. High-resolution TEM (HRTEM) images
(Fig. 4.22) show that MSPB with magnetic NPs enclosed in the PS core have
a narrow distribution and well-defined structure.
212 Ayyaz Ahmad et al.

Figure 4.22 HRTEM images (A) and enlarged HRTEM images (B) of SPB with magnetic
NPs enclosed in the PS core (Kaimin et al., 2010).

Figure 4.23 Schematic diagram of MSPB containing Pt NPs (Wu et al., 2012b).

MSPB has provided a promising and stable structure for the immobili-
zation of platinum NPs that can be easily recovered (Wu et al., 2012b).
Figure 4.23 shows the preparation of MSPB.
Ni NPs have been prepared in SPB nanoreactors by our group (Zhu
et al., 2011). The size of NPs can be tuned by changing the temperature dur-
ing preparation. Ni2þ replaced the counterions in SPB and then reduced to
form Ni NPs in the presence of NaBH4. TEM images of Ni NPs are shown
in Fig. 4.24.
Platinum (Pt) NPs were generated in PAEMH brushes containing SPB
(Wu et al., 2012a). The analysis of Pt SPB was done by X-ray diffraction
(XRD). The XRD pattern of as-prepared platinum composites showed
Progress in Polymer Nanoreactors 213

Figure 4.24 TEM images (A) and (B) of SPB containing Ni NPs with narrow size
distribution (Zhu et al., 2011).

Figure 4.25 XRD pattern for Pt NPs on SPB.

Bragg reflections at 2y ¼ 39.9
, 46.4
, 67.7
and 81.6
, which correspond

respectively to the **(111), **(200), **(220) and **(311) reflections of
the face-centered cubic structure typical of platinum Fig. 4.25.
TiO2 NPs were generated as photocatalysts by Lu et al. in the SPB con-
taining PS core and poly(styrene sulfonic acid sodium) as brushes (Lu et al.,
2009). Tetraethylorthotitanate was the precursor compound. Crystalline
anatase TiO2 NPs were produced at room temperature. After SPB were cal-
cinated at high temperature, mesoporous titania were observed. Manganese
dioxide (MnO2) NPs were prepared in SPB of poly(trimethyl ammonium
ethyl methacrylate chloride) brushes (Polzer et al., 2010). Ultrafine magnetic
214 Ayyaz Ahmad et al.

Figure 4.26 TEM images of the SPB with and without MNP: (A) SPB; (B) enlarged SPB;
(C) c-MSPB; (D) enlarged c-MSPB; (E) statistical size of MNP in c-MSPB; (F) r-MSPB;
(G) enlarged r-MSPB; (H) statistical size of MNP in r-MSPB. (Zhu et al., 2012).

NPs were prepared in PAA SPB nanoreactor through the conventional

coprecipitation method (Zhu et al., 2012). To lock the prepared NPs in
SPB, small amounts of N,N0 -methylenebisacrylamide (BIS) were always
used as crosslinkers. TEM images of SPB with and without magnetic NPs
are shown in Fig. 4.26.
Due to its nontoxicity, chemical stability and photocatalytic activity,
ZnO has attracted great attention recently. Our group has synthesized
well-defined ZnO NPs by using SPB as a nanoreactor. To increase the
amount of ZnO, multigeneration cycles were employed (Fig. 4.27).
Progress in Polymer Nanoreactors 215

Figure 4.27 Effect of multigeneration cycles on SPB size.

4.3. In catalysis
NPs illustrate completely different properties from their bulk form and
have become a very active research area in recent years due to their high
surface–volume ratio (Lu et al., 2007b; Malysheva et al., 2008; Polzer
et al., 2012; Proch et al., 2008; Sharma et al., 2007; Yu et al., 2007). An inert
support is required, however, to prevent aggregation during catalysis. SPB
has proved to be a suitable carrier for NP catalysts (Lu et al., 2007b; Mei
et al., 2005; Yan et al., 2006).
Au–TiO2 prepared and immobilized in SPB has been used as a catalyst in
the photocatalytic degradation of the organic dye Rhodamine B (128). The
rate constant is three to five times higher than that using pure TiO2. The
reaction kinetics of this reaction is measured at different times by UV–vis
spectroscopy, as shown in Fig. 4.28.
Our group has synthesized NPs of nickel and platinum on SPB con-
taining PAA and PAEMH, respectively (Wu et al., 2012a,b; Zhu et al.,
2011). They were used respectively in catalytic reduction reactions of
4-nitrophenol to 4-aminophenol and p-nitrophenol to p-aminophenol by
NaBH4. The correlation between the reaction rate constant and the concen-
tration and surface area of Ni NPs is shown in Fig. 4.29.
216 Ayyaz Ahmad et al.

Figure 4.28 Photodegradation of Rhodamine B catalyzed by SPB with Au–TiO2, as

observed by UV–vis spectroscopy (Lu et al., 2010).

Figure 4.29 Catalytic activity of Ni NPs. (A) Change of UV peaks with reaction time. (B)
The reaction rate constant as a function of total surface area of Ni NPs. (C) Decrease of
4-nitrophenol concentration at different Ni NP concentrations. (D) The rate constant as a
function of the concentration of Ni NPs (Wu et al., 2012a; Zhu et al., 2011).
Progress in Polymer Nanoreactors 217

Figure 4.30 Schematic of nanoalloys on SPB (Kaiser et al., 2012).

Kaiser et al. (2012) have prepared nanoalloys of Au and Pd on SPB

(Fig. 4.30). The kinetic analysis showed that the rate constant was enhanced
due to higher catalytic activity of the Au/Pd nanoalloy on the surface for the
model reaction of 4-nitrophenol.

4.4. In protein immobilization

Protein immobilization is an important issue for biomedical and biotech-
nological applications, including controlled drug delivery, protein separa-
tion, and biosensors. Smart polymers can manage protein immobilization
by the manipulation of environmental parameters (temperature, pH, ionic
strength, electric field, and light) (Mendes, 2008). SPB are an attractive
option for protein or enzyme immobilization (Jain et al., 2009).
Ballauff et al. reported their research on protein adsorption in SPB
(Anikin et al., 2005; Czeslik et al., 2004a; Haupt et al., 2005; Henzler
et al., 2007, 2010; Jackler et al., 2004; Rosenfeldt et al., 2004;
Wittemann and Ballauff, 2005, 2006; Wittemann et al., 2003a,b, 2006,
2007). They found that bovine serum albumin (BSA) was able to immobilize
in PAA SPB at low ionic strength (Fig. 4.31) (Czeslik et al., 2004b;
Wittemann et al., 2003a). Recently, we reported that the binding, aggrega-
tion, and releasing of proteins in cationic SPB can be tuned by ionic strength,
pH, and stoichiometry (Wang et al., 2013).
The release and uptake behavior of fluorescent protein (mEosFP) mol-
ecules on SPB has been studied (Anikin et al., 2005). Confocal laser scanning
microscopy images showed the binding of mEosFP in SPB at low ionic
strength and release of protein at higher ionic strength (Fig. 4.32).
218 Ayyaz Ahmad et al.

1200

tads (mg/g SPB)

800

400

0
0 4 8 12
Figure 4.31 Amount of adsorbed BSA per unit mass of SPB as a function of the protein
concentration left unadsorbed in solution. The changing parameter of the different cur-
ves is the concentration of added salt (NaCl). Symbols denote: filled squares, no added
salt; hollow circles, 32 mM; triangles, 57 mM; hollow squares, 107 mM; filled circles,
157 mM. The lines show the theoretical fits of the data (Wittemann et al., 2003a).

Figure 4.32 Confocal laser scanning microscopy images. (A) SPB without protein, (B)
SPB with immobilized protein at low ionic strength, (C) at high ionic strength (Anikin
et al., 2005).

5. CONCLUSION
The uninterrupted and flourishing development of SPB nanoreactors
has emerged as a new class of smart polymeric material. Its remarkable fea-
tures are offering a new dimension in the crossing fields of polymer science,
materials, chemistry, biomedical engineering, and chemical engineering.
A large number of SPB applications have been developed and many char-
acteristics have been revealed. This review has highlighted SPB synthesis
methods, functionalization, and its applications as nanoreactors in which
Progress in Polymer Nanoreactors 219

different NPs of metal or metal oxide can be prepared and proteins

immobilized. SPB as a novel nanoreactor has opened a new way to prepare
nanosized functional materials. In the future, more work should be done in
quick responsive and sophisticated SPB nanoreactors. New research can
focus on the industrialization of these nanoreactors for the benefit of
mankind.

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