1 s2.0 S0300944014000538 Main

Progress in Organic Coatings 77 (2014) 913948
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Progress in Organic Coatings
j our nal homepage: www. el sevi er . com/ l ocat e/ por gcoat
Review
Recent advances in ATRP methods in relation to the synthesis of
copolymer coating materials
Piotr Krl, Pawe Chmielarz
Department of Polymer Science, Faculty of Chemistry, Rzeszw University of Technology, Al. Powsta ncw Warszawy 6, 35-959 Rzeszw, Poland
a r t i c l e i n f o
Article history:
Received 31 October 2013
Received in revised form17 January 2014
Accepted 29 January 2014
Available online 25 February 2014
Keywords:
Polymer synthesis
ATRP
Copolymer coatings
Biomaterials
Bioactive surface
a b s t r a c t
Atom transfer radical polymerization (ATRP) is currently one of the most often used synthetic polymer-
ization methods to prepare well-dened copolymers with complex architecture. This review covers some
fundamentals of ATRP, presents new ATRP initiating processes with ppm amounts of copper catalysts and
various reducing agents together with recent developed electrochemically controlled ATRP, as well as
discusses ATRP enables to precise control over macromolecular structure, order, and functionality. More-
over, this review briey describes some of the copolymer coating materials that can now be prepared
e.g., protective coatings with increased hydrophobicity, functional bioactive surfaces and functional bio-
materials, as well as highlights some of the commercialization efforts currently underway. The research
activities in the last decade indicate that ATRP has become an essential tool for the design and synthesis
of advanced, noble and novel copolymer coatings.
2014 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 913
2. The most important mechanisms of the growth of polymer chains used in ATRP methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
3. Controlled polymer structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
4. Applications of copolymers with particular emphasis on coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 918
4.1. Protective coatings with increased hydrophobicity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 919
4.2. Antifouling surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 920
4.3. Antibacterial surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 928
4.4. Stimuli-responsive surface (micelles) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 929
4.5. Hydrogels (tissue engineering scaffolds) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 935
4.6. Microgel-core star polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 939
5. Comercial applications of copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 940
6. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941
1. Introduction
Recent needs ina range of protective coatings permanently con-
nected with natural materials such as wood and paper or with
ceramics and metal articles force the search for new polymeric
materials. However raw material limited possibilities and envi-
ronmental issues are directing the attention of researchers for
improving polymerization methods of the well-known and widely
applied such as vinyl monomers, as well as rawmaterials useful for
Corresponding author. Tel.: +48 661038877.

E-mail address: p chmiel@prz.edu.pl (P. Chmielarz).
producing condensationpolymers andadditive polymers e.g. PU. In
recent years, these needs have been additionally enhanced by the
need to develop newsynthetic biomaterials well cooperating with
the tissues of the human body. In our opinion, new polymeriza-
tion methods discovered in recent years allow for the production
of polymers with controlled macromolecular structure and they
are outgoing opposite these very specic applications of polymer
coatings. In addition less important is to use the new monomers,
and much more important is obtaining during the polymerization
step of even known vinyl monomers and acrylic newstructures of
such macromolecules. Latest methods in this regard, already well
developed fromthe side of preparative and theoretical explaining
kinetics and mechanism of their progress, but still poorly used in
0300-9440/$ see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.porgcoat.2014.01.027
914 P. Krl, P. Chmielarz / Progress in Organic Coatings 77 (2014) 913948
Notations
AA acrylic acid
AFM atomic force microscopy
AGET activators generated by electron transfer
ARGET activators regenerated by electron transfer
ATRP atomtransfer radical polymerization
BIBB 2-bromoisobutyryl bromide
Bpy 2,2
-bipyridine
CM cellulose membranes
CMU Carnegie Mellon University
CRP controlled radical polymerization
CuBr copper (I) bromide
CuBr
2
copper (II) bromide
CuCl copper (I) chloride
CuCl
2
copper (II) chloride
DI dispersity
DMAEMA 2-dimethylaminoethyl methacrylate
DMMSA 2-(methacryloyloxyethyl) ethyl-dimethyl-(3-
sulfopropyl)-ammonium
DMVSA N,N-dimethyl-N-(p-vinylbenyl)-N-(3-sulfopropyl)
ammonium
DP degree of polymerization
eATRP electrochemically mediated ATRP
EBIB ethyl 2-bromoisobutyrate
EGDMA ethylene glycol dimethacrylate
GMA glycidyl methacrylate
HEMA 2-hydroxyethyl methacrylate
ICAR initiation for continuous activators regeneration
LCST lower critical solution temperature
LRP living radical polymerization
MDI 4,4
-methylene diphenyl diisocyanate

ME 2-mercaptoethanol
Me
6
-TREN hexamethylated tris(2-aminoethyl)amine
MIP molecularly imprinted polymer
MPC 2-methacryloyloxyethyl phosphorylcholine
MUBIB -mercaptoundecyl bromoisobutyrate
MW molecular weight
MWD molecular weight distribution
NI normal initiation
NIP nonimprinted polymer
NIPAM N-isopropylacrylamide
OEG oligo(ethylene glycol)
OEGMA oligo(ethylene glycol) methacrylate
PBA poly(n-butylacrylate)
PDA poly(dopamine)
PDMS poly(dimethylsiloxane)
PEG poly(ethylene glycol)
PMDETA N,N,N
,N
,N
-pentamethyldiethlyenetriamine
PMMA poly(methyl methacrylate)
PES polyethersulfone
PPCPA poly(pentachlorophenyl acrylate)
PPPGMA poly(poly(propylene glycol methacrylate))
PS polystyrene
PSf polysulfone
PTMO poly(oxytetramethylene) glycol
PTX paclitaxel
PU polyurethane
PVDF poly(vinylidene uoride)
PVP poly(N-vinylpyrrolidone)
RA reducing agent
SAM self-assembled monolayer
SEM scanning electron microscope
SET-LRP single-electron transfer living radical polymeriza-
tion
SI-ATRP surface-initiated ATRP
SR reverse initiation
SR&NI simultaneous reverse and normal initiation
SS stainless steel
TEA triethylamine
QA quaternary ammonium
VBA vinylbenzoic acid
materials engineering are methods known under the general name
of atom transfer radical polymerization (ATRP). Therefore in the
presented publication we would like to drawattention to the latest
developments in this eld and to indicate the directions of applica-
tions of polymers with a very specic structure, not known before
a fewyears in the engineering of protective coatings.
This article reviews recent advances in the preparation of
copolymer coating materials using ATRP for biomedical and other
applications. The modication of polymer surfaces, hydrophobic in
most of the cases, is requiredfor multiple applications. For instance,
lowsurface energy polymeric materials do not adhere well to other
materials and need of further modication/surface treatment to
improve adhesion.
ATRP is one of the most powerful and versatile CRP pro-
cesses used for the synthesis of functional copolymers with
well-dened architectures, controlled molecular weights, and tun-
able sequences. It enables precise control over MW, MWD, and
functionality [14]. Block copolymers are an interesting class of
materials that possess different properties compared to those of
each individual homopolymer segments they are composed of.
As block length is playing a major role on the properties of the
block copolymers, effective control of the block lengths is impor-
tant and this can easily be achieved using different CRP methods
[5]. Most of the desirable properties of narrowMWD block copoly-
mers (synthesizedby living polymerizationor ATRP) originate from
their ability to form well-dened nanostructures with different
morphologies of tunable periodicity or size, and this provides the
primary driving force for the intensive interest in eld of coating
applications over the polydisperse copolymers (randomor alterna-
tive) synthesized by conventional radical polymerization. Narrow
MWD block copolymers (controlled) are more useful for coating
application rather than polydisperse random copolymers synthe-
sized by conventional radical polymerization. It results fromit, that
inregular arrangements, inwhicharrangingstructures results from
intermolecular interactions, exists a possibility of the simpler crys-
tallization as a result of stronger intermolecular interactions.
Recent advances in the synthesis of block copolymers have
focused on techniques that either enable the preparation of com-
pletely newmaterials or represent a substantial improvement with
respect to the existing methods in terms of scalability, environ-
mental friendliness, or scope. One observable trend is to design
experimental setups which allowfor the automated and optimized
synthesis of polymers andblockcopolymers. Another ongoingtopic
involves attempts to reduce the environmental impact of exist-
ing polymer syntheses. In ATRP reactions, the metal catalyst (most
oftenCu, as well as Fe, Ru, Ni, etc.) loading couldbe decreaseddown
to ppm levels through the use of a suitable additive for catalyst
regeneration, for example in ARGET process [6,7].
2. The most important mechanisms of the growth of
polymer chains used in ATRP methods
ATRP is one of the most rapidly developing areas of poly-
mer science, allowing to obtain effective control over molecular
weights, narrow molecular weight distributions, functionalities,
P. Krl, P. Chmielarz / Progress in Organic Coatings 77 (2014) 913948 915
architectures, and well-dened compositions [8,9]. ATRP processes
have evolved signicantly during the past 15 years and it has
strongly inuenced the development of many elds of polymer
science, invigorating great interest in controlled polymerizations
[10]. There are several reports on the synthesis of copolymers and
the study of their properties, as these copolymers are important
materials in the several elds of natural science, for example, col-
loid science and biochemistry, as well as in industrial elds [11,12].
Moreover, the interface of ATRP with biology has always been one
of the most attractive areas for applications due to ATRPs robust
nature and ability to growpolymers froma variety of surfaces [10].
The essential feature of original normal (NI) ATRP is con-
trolled by an equilibrium between a low concentration of active
propagating species and a larger number of dormant chains, pre-
dominately in the formof initiating alkyl halides/macromolecular
species (R
n
X, where R
n
represents growing polymer chain and X
is halogen atom) [13,14] (Scheme 1). The dormant species periodi-
cally react with the rate constant of activation (k
act
) with transition
metal complexes intheir lower oxidationstate (Cu(I)/L, where Cu(I)
represents the transitionmetal species inlower oxidationstate and
L is a ligand). After which, these species acting as activators to inter-
mittently formgrowing radicals (R
n
), and deactivatorstransition
metal complexes in their higher oxidation state, coordinated with
halide ligands Cu(II)/L (Scheme 1) [15].
The deactivator reacts with the propagating radical in a reverse
reaction (k
deact
) to re-form the dormant species and the activa-
tor. ATRP is a catalytic process and can be mediated by many
redox-active transition metal complexes [1]. Upon addition of the
intermediate radicals to monomers, polymer chains growwith the
rate constant of propagation k
p
. Termination reactions (k
t
) also
occur in ATRP, mainly through radical coupling and disproportion-
ation. However, a very small percentage of polymer chains undergo
termination in a well-controlled ATRP. This is due to the low con-
centration of active propagating radicals and higher concentration
of dormant species, whichminimizes termination. Althoughcopper
is most commonly used metal catalyst in ATRP [1620], iron com-
pounds [2128], which are generally considered to be less toxic,
can also be used, especially for biomedical applications [29,30].
Actually, other various metal complexes have been successfully
employed to mediate ATRP, including Ru [31,32], Ni [33,34], Ti
[35,36], Re [37], Mo [38], Co [39], and Os [40,41].
However, NI ATRP has one notable limitation that is the catalyst
used is sensitive to air and other oxidant. In order to overcome
this drawback of normal ATRP, more recently, Matyjaszewskis
group has developed an improved reverse (SR) ATRP technique
[9]. Subsequently, SR ATRP was developed that started by addition
of the transition metal complex in its higher oxidation state, such
as Cu(II)/L complexes, which was then converted to the activator
Cu(I)/L complexes by reaction with a standard free radical initiator
(II), for example benzoyl peroxide (BP) or 2,2
-azoisobutyronitrile
(AIBN) [4244] (Scheme 2).
After deoxygenation, the polymerizationis initiatedby the reac-
tion of Cu(II) with radicals, generated by thermal decomposition
of conventional thermal initiators. This circumvents the problem
associated with oxidation of catalysts [45].
SR&NI ATRP was developed to take advantage of the ability to
use more active catalyst complexes with addition of a relatively
R
M
.
X Cu(II)/L Cu(I)/L X R
R R
k
act
k
deact
+
k
p
k
t
+
n n
n n
(1)
Scheme 1.
M
I
.
I I
R
M
.
R R
+
k
p
k
t
+
n n
n n
k
act
k
deact
(2)
Scheme 2.
M
I
.
I I
R
M
.
R R
+
k
p
k
t
+
n n
n n
ATRP Initiator
k
act
k
deact
(3)
Scheme 3.
larger amount of alkyl halide initiator concurrently with a small
amount of radical initiators [15].
In a SR&NI initiation procedure, ATRP initiators, alkyl halides
or halogen-terminated macroinitiator, are added to the reaction
together with a conventional thermal initiator II (Scheme 3). Both
reagents contribute to the ATRP equilibrium, so that the relative
amount of catalysts can be dramatically decreased, and the syn-
thesis of block copolymers can be achieved [45].
SR&NI ATRP provided a way to reduce the catalyst concentra-
tion without sacricing the level of control over polymerization.
While SR&NI is a signicant improvement over SR ATRP, the SR&NI
process has an intrinsic deciency when it is used to synthesize
block copolymers [45]. A limitation of SR&NI was the formation of
a small fractionof polymer chains initiatedbythe addedfree radical
initiator [15].
In order to overcome this limitation, and prepare a pure block
copolymer without contamination by homopolymers, an initia-
tion procedure named AGET was developed for ATRP. Instead of
a conventional radical initiator, a RA was used to react with the
Cu(II) complex and to generate the activator without involvement
of organic radicals or formation of reaction products which could
initiate newchains (Scheme 4) [45,46].
SR&NI evolved into AGET where the added deactivator was acti-
vated by various RA including Mt
0
species rather than a radical
initiator [47]. In a typical AGET ATRP system, the activator (Cu(I)
species) is rst rapidly oxidized by oxygen to the Cu(II) species, but
the latter is quickly reduced to the Cu(I) state in the presence of a
RA. There is an induction period during which air is consumed, and
eventually the polymerization starts. This process has been suc-
cessfully used to prepare well-dened products in organic media
and also in miniemulsion. Unfortunately, it is difcult to estimate
the exact amount of RA needed [48].
R
M
.
R R
X Cu(II)/L
+
k
p
k
t
+
n n
n n
RA
k
act
k
deact
(4)
Scheme 4.
I
.
R
M
.
R R
I I I X
+
k
p
kt
+
n n
n n
k
act
k
deact
(5)
Scheme 5.
In addition to normal ATRP, the development of AGET ATRP,
which enables polymerizations to be conducted without freeze-
pump-thaw cycles, has poised AGET ATRP to be carried out by
biologists and other scientists in jars on the bench top [8].
Infact, basedonthe development of SR&NI andAGETtechniques
discussed above, newinitiation method, such as ICAR, were devel-
oped at about 8 years ago [49]. In this system, a large excess of RA
(free radicals from thermal initiator) were used for a continuous
regeneration of very lowlevels of catalyst activators. By using ICAR
initiation technique, the amount of Cu catalyst necessary for an
ATRP was lowered fromseveral thousand ppmunder normal con-
ditions to <50ppm while still maintaining excellent control over
MWand MWD [45,5052].
The initiators for ICAR procedure could be considered as a
reverse ARGET ATRP (as shown in Scheme 5). In ICAR ATRP, a
source of organic free radicals is employed to continuously regen-
erate the Cu(I) activator, which would otherwise be consumed in
termination reactions, when catalysts are used at very lowconcen-
trations [15,53,54]. Anadvantage of initiating anATRP withanalkyl
pseudohalide is that no newchains are formedby addedradical ini-
tiators and higher molecular weight copolymers can be prepared
[15].
To overcome the main problem of AGET ATRP difcult to
estimate the exact amount of RA, system known as ARGET ATRP
was discovered (Scheme 6) [55]. This newmethod provides a con-
tinuous controlled polymerization with a signicant reduction of
the amount of copper-based catalyst complex (<50ppm) due to a
constant regeneration of the Cu(I) activator species by RA, which
compensate for any loss of Cu(I) by termination [5659]. A variety
of RA, such as tin(II) 2-ethylhexanoate [60], glucose [9], ascor-
bic acid [6163], hydrazine [64], thiophenol [65], TEA [65], Cu(0)
[57], or phenols [64] have been successfully used to synthesize a
wide variety of polymers with varying architecture and reactiv-
ity. Lowering the concentration of the catalysts not only results
in,greener polymerization processes but also allows for the syn-
thesis of polymers with high MWand high chain-end functionality
[6668].
ARGET ATRP was successfully applied to relatively nonpolar
monomers (e.g., styrene, butyl acrylate, and methyl methacrylate)
.
R
M
R R X Cu(II)/L
+
k
p
k
t
+
n n
n n
oxidized form of RA + HX
+
excess of RA
k
act
k
deact
(6)
Scheme 6.
Scheme 7.
[48], for the preparation of a variety of polymeric materials with
different structures and architectures including homopolymers,
well-dened block copolymers, and development of a scalable
process for preparation of molecular brushes on a at surface
[8].
Applicationof electrochemistry toATRPcouldbe another break-
through that will enable expansion to newapplications [69]. In all
ARGET and ICAR processes, RA are oxidized, generating some side
products: new chains in ICAR, dehydroascorbic acid, and tin(IV)
species, etc., in ARGET. These oxidized species might be less benign
than the original RA. Therefore, it would be of interest to avoid
using chemicals as RA and replace them by electrons, specically
electrical current. This is the concept of electrochemically medi-
ated (eATRP) in which the ratio of the concentration of activator
to deactivator is precisely controlled by electrochemistry. Several
parameters, such as applied current, potential, and total charge
passed, can be controlled in eATRP to allowselection of the desired
concentrationof the redox-active catalytic species. The mechanism
of ATRP mediated through electrochemical control over the ratio of
Cu(I)/Cu(II) and (re)generation of activators is shown in Scheme 7
[15].
A targeted amount of the air-stable Cu(II)/L catalyst complex
can be electrochemically reduced to Cu(I)/L activators to start a
controlled polymerization. In the absence of mass transport lim-
itations, the rate of reduction is dictated by the applied potential
(E
app
), enabling ne-tuning the polymerization rate by the gener-
ated ratio of Cu(I)/Cu(II) [7072]. This means that polymerizations
can be also stopped and restarted any time simply by switching
reversibly from a cathodic to an anodic current [73], by changing
the applied potential (E
app
) [15].
Meanwhile in 2006, Percec et al. [74] proposed that SET-
LRP undergoes an outer-sphere electron transfer process and has
very low activation energy. In their pioneering studies, electron
donors such as Cu(0)-wire or Cu(0) prepared in situ from the
disproportination of Cu(I) into Cu(0) activator, and Cu(II) deac-
tivator in a combination of ligand and solvent were used in the
living polymerization of functional monomers containing elec-
tron withdrawing groups such as methacrylates and acrylamides
[75]. Heterolytic dissociative electron transfer is one of the major
differences between SET-LRP and ATRP, but it is not the most
prominent. The most critical difference is that SET-LRPrelies ondis-
proportionation to generate the Cu(II) deactivator, whereas ATRP
relies on persistent radical effect via irreversible termination of
radicals in the initial, nonstationary stage of the polymerization.
This implies that termination is more signicant in ATRP than
in SET-LRP [36,7487]. It should be noted that the mechanisms
concerning the role of Cu(0) in this controlled/living polymeriza-
tion method have been further investigated by Matyjaszewskis
group [14,8893].
3. Controlled polymer structures
ATRP, as other CRP methods, provides a versatile toolbox for
preparation of various polymers with precisely controlled macro-
molecular architectures [73].
This includes polymers with controlled topology, ranging from
linear chains with precisely controlled dimensions and controlled
DI to various branched structures formed by copolymerization of
macromonomers, graftingontofunctional backbones, graftingfrom
multifunctional backbones, copolymers formed using di- and mul-
tifunctional initiators [15].
Fig. 1 illustrates some examples of polymers with controlled
topology prepared by ATRP. It is essential, that it was not possi-
ble to receive these structures usually in conventional free radical
polymerization methods.
There are many examples of controlling polymer chaintopology
to form branched architectures including star polymers (Fig. 1b),
preparedusingeither core-rst, grafting-toor arm-rst approaches
[94].
The core rst approach, starting froma multifunctional core and
a progressive ATRP growth of the arms, can generate well-dened
stars andevenstar-block copolymers. Alternatively, ina grafting-to
approach, functional macroinitiators can react with a core contain-
ing several complementary functionalities [95]. The latter relies on
using macroinitiators or macromonomers in an ATRP with divinyl
crosslinking agents, under appropriate conditions; instead of form-
ingmacroscopic gels/networks (Fig. 1c) areformedinhighyieldand
with high uniformity [96].
ATRP has been also used for synthesis of hyperbranched poly-
mers (Fig. 1d) and even for dendritic systems [97,98].
One can also prepare comb-like polymers (Fig. 1e) by graft-
ing from, onto or through, using macromonomers [99]. Comb
copolymers represent another class of branched architectures.
Very high graft density in graft copolymers leads to the forma-
tion of molecular bottle brushes [100]. When these densely grafted
copolymers deposited on surfaces, they can change conformation
depending on the surface energy, they can move on low-energy
surfaces, but depositionon a high-energy surface can introduce a
tremendous degree of tension on the backbone that might result in
a backbone cleavage [101].
ATRP was also used to precisely control chain composition and
prepare segmented (block and graft) copolymers as well as peri-
odic and gradient systems [15]. Fig. 2 presents some examples of
polymers with controlled composition prepared by ATRP.
Concerning polymer composition, one can use ATRP to prepare
not only homopolymers (Fig. 2a) but also statistical (random)
(Fig. 2b) copolymers from monomers with similar reactivities
[73]. The list of monomers successfully homopolymerized by ATRP
includes various styrenes, acrylates, methacrylates, acrylamides,
and acrylonitrile as well as vinyl acetate and vinyl chloride [15].
Block and graft copolymers (Fig. 2c and d) are the most com-
mon form of segmented copolymers. For the sake of reliability
should say here that considerable potential in the synthesis of
these copolymers has already largely used in industry, provide
new methods of the coordination polymerization based on a het-
erogeneous andhomogeneous Ziegler-Natta catalysts, metallocene
and post-metallocene catalysts, however up to nowthese methods
are limited mainly to olens and diene monomers [102104]. Pre-
sented above in the chapter two of the ATRP methods admittedly
up till now do not let getting of iso- and syndiotactic vinyl poly-
mers, but the architecture of macromolecules obtained by these
methods can be very diverse, and they concern the possibility of
the synthesis a lot of vinyl polymers modifying in the different
degrees structures of different polymers including condensation
Fig. 1. Examples of polymers with controlled topology prepared by ATRP.
Fig. 2. Examples of polymers with controlled composition prepared by ATRP.
resins. The same technique of the copolymerization it is not so
complicated in terms of equipment, like in the case of coordination
polymerizations.
Block copolymers can be formed by sequential addition of
comonomers to an ongoing reaction or by segmental coupling
(using, for example, click chemistry), use of mechanistic transfor-
mation(from/toATRPandionic, coordinationor polycondensation)
or even 2-directional concurrent growth using different polymer-
ization mechanisms for the preparation of each segment. Moreover
graft copolymers can be prepared by grafting from, grafting onto,
and grafting through [73].
Gradient copolymers (Fig. 2f) form a new class of copolymers
with a composition continuously changing along the chain length
that a rose with the advent of CRP. Interest in gradient copolymers
originates intheir unique properties suchas surfactants due totheir
specic critical micellar concentrations and broad glass transition
temperature [105].
ATRP is tolerant of many functionalities and can also be used to
successfully incorporate functionalities after polymerization [15].
They include polymers with one functional group (this group
could be also a polymerizable group as in macromonomers) but
also with two groups, as in telechelics with the same or different
functionalities (Fig. 3ac). They can be extended to prepare multi-
functional polymers (Fig. 3d), with either regular structure such as
in stars and brushes or a less regular structures in those based on
hyperbranchedstructures. It is possible to place functionality at the
ends of the chains (Fig. 3e) or at a specic site of a macromolecule
(Fig. 3f), generally in a center or a branch point [15].
ATRP is tolerant to many functional groups such as hydroxy,
cyano, amino, amido, esters and others [2]. Functional groups in
ATRP can originate from the initiator or from a comonomer but
can also be incorporated by replacing end terminal halogens [106].
Functional groups can modify the polymers properties but can
also be used for cross-linking, chain extension, and supramolecu-
lar assembly basedonweaker interactions via hydrogenbonding or
weak covalent bonding. Additionally, some functional groups can
be sensitive to temperature, light, redox, or pH, leading to smart
responsive materials [101]. These groups can be part of monomers
and end groups but can also be incorporated after polymerization,
via click reactions [107].
The nal properties of many materials are dened not only by
architecture of a single macromolecule but by their self-assembly
to various nanostructured materials. In addition, controlled pre-
assembly is also possible by surface patterning, grafting from
various functional surfaces and even from linear polymer chains.
There are manymorphologies available fromself-assemblyof block
copolymers, dependingonthe blockorder, interactions andvolume
fractions that constitute spheres, cylinders and lamellae in various
combinations [108].
4. Applications of copolymers with particular emphasis on
coatings
In the solid state, block copolymers coatings can microphase
separate to form well-dened self-assembled structures of pre-
dictable size. The nature of the morphology is dependent on many
factors, including the architecture of the block copolymer (e.g.
di-block, tri-block or miktoarm star), the DP of each block, inter-
actions between blocks, and the interactions of each block with
the environment, as well as sample processing. In the simplest
situation of an block copolymer, the known thermodynamically
stable solid-state morphologies include spherical, cylindrical and
Fig. 3. Examples of polymers with functional groups placed in different positions.
C C Br
C H
3
C H
3
O
O
N C
H
O
N (CH
2
)
4
O
n
O
O
H O
H
CH
2
CH
2
N N
H
C
O
O
m
O (CH
2
)
2
(CH
2
)
2
C C Br
CH
3
CH
3
O
O
(8)
Scheme 8.
lamellar structures. When multiblock copolymers and branched
block copolymers are considered, a large number of complex mor-
phologies becomes possible. The material coatings properties of
block copolymers are derived from the physical characteristics of
the constituent homopolymer blocks [6].
4.1. Protective coatings with increased hydrophobicity
Drawing up a few years ago, the review about applying PU in
the modern materials engineering, for which we paid attention to
the importance of the ability of these polymers for preparation of
polymer coatings with increased hydrophobicity. It is possible to
obtain it by building into a linear PU segments containing uo-
rine or different alkylammonium groups present in the ionomer
coatings produced on the base of ecological waterborne PU lac-
quers [109]. ATRP methods are creating additional possibilities in
this area, because theyhas beenusedextensivelyinthe preparation
of various tri-block copolymer surfaces directed to use as a func-
tional biomaterials as well as special protective coatings to polar
materials (old prints, wood or ceramics).
Block copolymers are composed of two or more chemically
distinct polymer chains linked together at one or more junction
points through covalent or noncovalent bonds. As a consequence
of the inherent immiscibility of different polymer segments, block
copolymers undergo microphase separation in the bulk phase and
in thin lms. In solution, block copolymers will formmicelles when
the solvent is selective for one of the blocks. Most of the desirable
properties of block copolymers originate fromtheir ability to form
well-dened nanostructures with different morphologies of tun-
able periodicity or size, and this provides the primary driving force
for the intensive interest in this eld [6].
However, tri-block copolymers have sparked much interest and
their potential has been realized in many areas involving the elds
of chemistry, physics, materials science, as well as the biological
and medical sciences. Tri-block copolymers are an interesting class
of materials that possess different properties compared to those of
each individual homopolymer segments they are composed of. As
block length is playing a major role on the properties of the block
copolymers, effective control of the block lengths is important and
this can easily be achieved using different CRP methods [5].
Tri-block copolymers with using different PU based macroini-
tiator were already obtained through ATRP classical mechanism
[110,111]. However, this method was arduous because of the
necessary to degassed of reaction mixture. Recently, we have
demonstrated that ARGET ATRP can be successfully used for the
synthesis of tri-block copolymers using PU as a macroinitiator
in the presence of limited amounts of air, with omitting the
deoxygenation process [5,112]. Realizing this concept, recently
we synthesized newtypes of poly(urethane-methacrylate) copoly-
mers, using the specially made urethane macroinitiators: bromine
[5] and tetraphenylethane [112], capable of reacting with
methacrylate monomers.
First mentioned 2-methyl-2-bromopropionate terminated
(tertiary bromine-terminated) PU macroinitiator (MBP-PU-MBP)
(formula 8) was synthesized from 1mol of PTMO, 2mol of
MDI, and 2mol of 2-hydroxyethyl-2
-methyl-2
-bromopropionate
(HMB) (Scheme 8) [5].
While, tetraphenylethane termined PUmacroinitiator (TPE-PU-
TPE) (formula 9) was synthesizedfrom1mol of PTMO, 2mol of MDI,
and 2mol of 1,1,2,2-tetraphenylethane-1,2-diol (TPED) (Scheme 9)
[112].
PU structures affect the improvement in mechanical proper-
ties of that kind of copolymers, while segments of PMMA are
used to hydrophobization of PU surface. Poly(urethane-acrylate)
copolymers are nding application as biomaterials, among others
biocompatible implant in tissue engineering [113], hydrophobic
antimicrobial coating [114] and drug delivery in the formof appro-
priately formed micellar structures [115].
However, as part of work [116] we carried the comparative
study of these materials in terms of their resistance to hydrolytic
degradation in the environment of physiological liquid similar to
the blood plasma. Performed examinations conrm that replace-
ment of the urethane segments by more hydrophobic methacrylic
segments contributes to increase the resistance to hydrolysis of
such block copolymers, because of high resistance to biodegrada-
tion in conditions of their long contact with physiological liquids
and tissues of living organisms. Meanwhile, by using confocal
microscopy (Fig. 4) method demonstrated, that it is highly variable,
which has a large inuence to the quality of biomaterial, because
in places of the inequality or structural dislocation, and faults of
phases built from segments of different polarity can be initiated
degradation processes, causing pathological changes in the organ
tissues being in contact with these areas.
More recently, Chatterjee et al. [117] describe the synthesis of
different block copolymers of unsaturatedandsaturatedpolyesters
with methyl methacrylate with well-dened molecular weight and
narrow DI by combination of condensation polymerization and
ATRP.
In the case of unsaturated-polyester-based block copolymers
the main chain double bond in the polyester backbone remains
almost unaffected during ATRP. The unsaturated block copolymers
are crosslinkable and can form networks upon. These copolymers
might be interesting candidates for coatings with better overall
properties than those based on neat polyesters. High-molecular-
weight polyesters or polyester/polyurethanes have appreciable
mechanical properties such as high tensile strength together with
COC N
H
O
N (CH
2
)O
4
n
O
O
H O
H
CH
2
CH
2
N N
H
C
O
O
m
C O C
O
C C O C
O
(9)
Scheme 9.
Fig. 4. Pictures of the surface of poly(urethane-methacrylate) copolymers obtained by using MBP-PU-MBP macroinitiator before (a) and after (b) exposure in physiologic
salt solution, as well as surface of copolymers obtained by using TPE-PU-TPE macroinitiator before (c) and after (d) exposure in physiologic salt solution, were taken for the
objects 320m320mand with magnication 50 [116].
exibility. But the presence of ester linkages in the backbone of
polyesters makes them vulnerable to acids/bases. On the other
hand, poly(meth)acrylates are better abrasion resistant, hydrolyti-
cally stable with superior mechanical properties [117].
4.2. Antifouling surface
As it is the surface that rst comes into contact with the biologi-
cal environment, thesubstratesurfacemust bemodiedtorender it
resistant to protein adsorption and cell adhesion. Thus, it is of great
importance to functionalize the substrate surface with antifouling
coating to improve the performances of biomedical devices and
biosensors [118].
ATRP has been widely utilized to impart various substrate
surfaces with antifouling properties, such as OEGMA (formula 10a)
[119136], GMA (formula 10b) [129,137,138], HEMA(formula 10c)
[133,135,139146], DMAEMA (formula 10d) [147149], as well as
zwitterionic monomers of DMVSA(formula 10e), DMMSA (formula
10f), MPC (formula 10g) [150152], sulfobetaine methacrylamide
(SBMAM) (formula 10h) [153] and sulfobetaine methacrylate
(SBMA) (formula 10i) [133,154,155] on magnetite nanoparticles
[119,123], silicon [120,124,126,129,133135,141,142,144,145,
149,152,153,155,156], titanium [121,155], nylon membrane
[139], PSf [138,147,154,157,158], cellulose [143,150], gold
[122,128,146,155], PVDF [127,136,140, poly(tetrauoroethylene)
(PTFE) [137], PDMS [148] and SS [151] (Scheme 10).
More recently, PSf lms were functionalized with block copoly-
mers containing PBA as anchor block which is able to rmly tether
the biocidal quaternized poly(2-dimethylaminoethyl methacry-
late) (PDMAEMAq) to the surface (Scheme 11). Block copolymers
were synthesized using sequential ATRP and quaternization with
methyl and/or octyl groups rendered the polymers biocidal.
Upon reversible swelling of the PSf surface layer in the adsorp-
tion/entrapment process, incorporation of the block copolymer is
anticipatedto be stable. Biocidal properties of the polymers incom-
bination can be applied to non-porous or porous objects in various
shapes result in a straight forward strategy to render polymeric
materials antimicrobial [147].
(10)
O CH
2
CH
2
O CH
3 n
C H
2
C
CH
3
C O
a)
O CH
2
CH
2
OH
C H
2
C
CH
3
C O
c)
S O
O
O
O CH
2
CH
2
N
+
C H
2
C
CH
3
C O
CH
2
CH
3
CH
3
CH
2
CH
2
f)
O CH
2
CH
2
C H
2
C
CH
3
C O
O P O
O
O
CH
2
CH
2
N
+
CH
3
CH
3
CH
3
g)
C H
2
C
CH
3
CH
2
N
+
CH
2
CH
3
CH
3
CH
2
CH
2
S O
O
O
e)
O CH
2
CH
2
N
C H
2
C
CH
3
C O
CH
3
CH
3
d)
O CH
2
CH
C H
2
C
CH
3
C O
O
CH
2
b)
S O
O
O
CH
2
CH
2
CH
2
O
C H
2
C
CH
3
C O
NH CH
2
CH
2
CH
2
N
+
CH
3
CH
3
h)
S O
O
O
CH
2
CH
2
CH
2
CH
2
CH
2
N
+
CH
3
CH
3
O
C H
2
C
CH
3
C O
i)
Scheme 10.
Recently[150], threezwitterionic polymers, includingpoly(N,N-
dimethyl-N-(p-vinylbenyl)-N-(3-sulfopropyl)ammonium)
(PDMVSA), poly(2-(methacryloyloxyethyl) ethyl-
dimethyl-(3-sulfopropyl)-ammonium) (PDMMSA), and
poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) were
grafted from CM via SI-ATRP. The SI-ATRP was performed by a
two-step process as shown in Scheme 12. The rst step is the
esterication of hydroxyl groups with BIBB to obtain initiator
functionalized CM(CM-Br) (Scheme 12a). Typically, CMsubstrates
were immersed in tetrahydrofuran (THF) solution containing TEA
and DMAP (2-dimethylaminopryridine), after which BIBB was
added into the mixture. In the second step (Scheme 12b), the
SI-ATRP from CM, was performed using CM-Br sheets, CuBr, Bpy
and appropriate monomer (DMVSA, DMMSA or MPC).
The zwitterionic polymer modied surfaces are more
hydrophilic than the original CMsurface (Fig. 5).
All the zwitterionic surfaces have improved resistance to non-
specic protein adsorption and possess excellent resistance to
platelet adhesion. Moreover, the PDMVSA and the PDMMSA mod-
ied surfaces were as effective as the PMPC modied surface at
preventing protein adsorption and platelet adhesion [150].
Meanwhile Yang [151] has developed functionalization of SS
surface with MPC using barnacle cement (BC) as surface anchor
for click reactions. Antifouling zwitterionic PMPC polymer brushes
Scheme 11.
Scheme 12.
were grafted from the thiol-functionalized SS-BC surface (SS-
thiol surface) via thiolene photopolymerization. The zwitterionic
SS-PMPC surfaces reduced bovine serum albumin adsorption sig-
nicantly and inhibit the adhesion of Gram-negative E. coli and
Gram-positive S. epidermidis (Fig. 6). This proves that surfaces
functionalization of metals have potential biomedical applications
[151].
MorerecentlyLi et al. [129] preparedPOEGMA-b-PGMAdi-block
copolymers on silicon wafers modied bioactive by SI-AGET ATRP
method. Scheme 13 shows the stages in the synthesis of antifoul-
ing brushes: (a) immobilization of OH groups on Si surface, (b)
amino-functionalization of silicon substrates, (c) immobilization of
bromo-thiol initiator on Si surface, (d) SI-AGET ATRP of POEGMA
brushes on Si surface and (e) di-block POEGMA-b-PGMA brushes
on Si [129131].
As an oxygen-tolerant LRP process, AGET ATRP allows precise
control of the length of each block in the copolymer and thus of the
copolymer layer thickness, thus giving control over the bioconju-
gation reactions. Different types of biomolecule can be conjugated
to these brush layers by reaction of PGMA epoxide groups
with amino groups in the biomolecule, while POEGMA, which
resists nonspecic protein adsorption, provides an antifouling
environment [129].
Authors were stated that surfaces with POEGMA layers were
protein resistant, while the quantity of protein conjugated to the
di-block copolymer modied surfaces increased with increasing
PGMA layer thickness (Fig. 7).
The activity of lysozyme conjugated on the surface could also be
controlled by varying the thickness of the copolymer layer. When
biotin was conjugated to the block copolymer grafts, the surface
remained resistant to nonspecic protein adsorption but showed
specic binding of avidin. These properties, that is, well-controlled
quantity and activity of conjugated biomolecules and specicity
of interaction with target biomolecules may be exploited for the
improvement of signal-to-noise ratio in sensor applications. More
generally, such surfaces may be useful as biological recognition
elements of high specicity for functional biomaterials [129].
Rodriguez-Emmenegger et al. [122] prepared
poly(oligo(ethylene glycol) methacrylate)-b-poly(carboxybetaine
acrylamide) (POEGMA-b-PCBAA) di-block brushes in phosphate-
buffered saline (PBS), fetal bovine (FBS) and calf sera (CS) from
a MUBIB self-assembled monolayer (SAM) immobilized on gold
Fig. 5. Water contact angle images of CM(a), CM-Br (b), CM-g-PDMVSA (c), CM-g-PDMMSA (d), and CM-g-PMPC (e) surfaces [150].
Fig. 6. SEM images of the (a, b) pristine SS, (c, d) SS-PMPC surfaces after exposure to E. coli (5107cells/mL; a and c) and S. epidermidis (5107cells/mL; b and d) for 4h
[151].
Scheme 13.
substrate (Au-SAM). A linear increase of the thickness with poly-
merization time was achieved using a catalytic system based
on CuCl/CuBr
2
/Bpy and CuBr/CuBr
2
/Me
4
Cyclam (N,N,N
,N-
tetramethyl-1,4,8,11-tetraazacyclotetradecane). Scheme 14 shows
the stages in the synthesis of antifouling brushes: (a) SAM of
bromo-thiol initiator on Au surface, (b) POEGMA brushes on Au
surface and (c) di-block POEGMA-b-PCBAA brushes on Au [122].
The prepared brushes showed excellent antifouling properties,
resisting the fouling even of undiluted complex biological media.
Moreover Sui et al. [140] have reported the antifouling prop-
erty of PVDF ultraltration (UF) membrane incorporating the
amphiphilic copolymer additive, PVDF-g-PHEMA synthesized via
ATRP (Scheme 15). To overcome the excellent chemical stability of
PVDF initiated via ATRP, bromine halide initiator (BIBB) was immo-
bilized onto the PVDF polymer pretreated by Fenton reagent (H
2
O
2
and FeSO
4
). PVDF-g-PHEMA copolymer had been synthesized by
ATRP, using a CuBr/CuBr
2
/PMDETA catalytic systembased with an
activated bromide as initiator, which was used successfully as a
surface-segregating additive to impart improved ux and fouling
resistance toPVDF-basedUF membranes. Duringcasting, the PVDF-
g-PHEMA additive segregates to form a PHEMA brush layer on all
blend membrane surfaces, including internal pores.
Moreover, the most commonly used antifouling materials are
PEG [134,159164] and OEG on PES bers [158], SS [160], PDMS
[163] and superparamagnetic iron oxide nanoparticles (IONPs)
[164]. PEG and its derivatives exhibit good antifouling effects to a
wide varietyof proteins, suppress platelet adhesion, andreduce cell
attachment and growth. Conventional methods for immobilizing
PEG coatings on substrates include direct attachment of self-
assembled PEG monolayer to surfaces, graft polymerization of PEG
monomers to a polymer backbone, adsorption of PEGblock copoly-
mers at multiple sites on the surface [165].
For example, Zhao et al. [159] have synthesized well-
dened block copolymers, poly(ethylene glycol) methyl ether-b-
poly(styrene) (mPEG-b-PS) using ATRP (using mPEGBr as the
macroinitiator), then used as amphiphilic additives to modify
PES hollow ber membranes to improve the antifouling property
(Scheme 16).
The hydrophilicity and the water ux of the modied mem-
branes increased with the decrease of the molecular weight of PS
blocks in the copolymers. The ux recovery property of the PES
membranes was signicantly enhanced, indicating that the modi-
edhollowber membranes couldbepotentiallyusedfor favorable
long-termutilization [159].
More recently, Jeong et al. [166] have synthesized PHA-b-
PLGA block copolymer (Scheme 17) composed of hyaluronic acid
(HA) as a hydrophilic block and dl-lactide-co-glycolide (LGA) as a
hydrophobic one for antitumor targeting.
Amphiphilic polymers such as block or graft copolymers and
hydrophobized polysaccharides cannormally formself-aggregated
nanoparticles or polymeric micelles. Especially, due to their unique
structures, block or graft copolymer generally forms a coreshell
structure, i.e., the hydrophilic domain forms an outershell and
the hydrophobic domain forms a hydrophobic inner-core via self-
assembly. Furthermore, the advantages of this structure are that
hydrophobic anti-cancer agents canbeincorporatedintothecoreof
Fig. 7. AFMimages of surfaces after water treatment [129].
the nanoparticles; the hydrophilic domain acts as a defense mem-
brane against attack by protein absorption [167]. Followed by the
preparation of coreshell type nanoparticles containing an anti-
cancer agent, Jeong et al. [166] have incorporated of doxorubicin
(DOX) to PHA-b-PLGA block copolymer.
Inparticular, one of the mainadvantages of PHA-b-PLGAcopoly-
mer nanoparticles is that HAsegment canbe freely directed toward
the outer-environment while the PLGA domain is in charge of
drug incorporation. The fact that HA is exposed on the surface
of nanoparticles may be helpful in targeting CD44 receptor of
Scheme 14.
Scheme 15.
(16)
Br C
O
C
CH
3
CH
3
Br C
O
O C
CH
3
CH
3
Br CH
2
CH
2
C H
3
O CH
2
CH
2
O
n
CH
2
CH
2
OH C H
3
O CH
2
CH
2
O
n
CH
2
Cl
2
C
O
O C
CH
3
CH
3
CH
2
CH
2
C H
3
O CH
2
CH
2
O
n
CH CH
2
Br
m
C
O
O C
CH
3
CH
3
Br CH
2
CH
2
C H
3
O CH
2
CH
2
O
n
+
a)
TEA
DMAP
mPEG-Br BIBB mPEG
b)
mPEG-b-PS mPEG-Br
CuBr/PMDETA
St
Scheme 16.
tumor cells. Flow cytometry data also showed similar results,
indicating that the uorescence intensity of tumor cells treated
with nanoparticles was signicantly decreased when CD44 recep-
tor was blocked. PHA-b-PLGA nanoparticles were able to target
CD44-overexpressing tumor cells via receptor-mediated endocy-
tosis [166].
Wang et al. [128] have developed gold nanoparticle layers of
different roughness modied with TD05 aptamers (Au-APT), for
potential applications inthe isolationandenrichment of circulating
tumor cells (CTCs).
First, the gold surface was modied with MUBIB by a self-
assembling method to introduce bromine groups (Scheme 18)
[168]. In the second step (Scheme 18b), POEGMA-modied Au sur-
faces had been synthetized by SI-ATRP, using a CuCl
2
/Bpy/ascorbic
acid system with an activated bromide as initiator on gold
surface. In the subsequent stages, POEGMA-modied Au sur-
faces were treated with N,N
-disuccinimidyl carbonate (DSC)

(Scheme 18c) and immersed in aptamer solution (3
end modi-
ed with amino group) to give the APT-modied Au-g-POEGMA
surfaces (Scheme 18d) [128].
In mixtures of Ramos (CL1012, B-cell, human Burkitts lym-
phoma) and CEM (CL1014, T cell line, human ALL) cells under
serum-free conditions, the density of Ramos cells on the roughest
Au surface was 19 times that of CEM(Fig. 8) [128].
C
O
CH
H
n
O CH O C
O
CH
CH
3
O C
O
CH
H
l
O C
O CH
3
NH (CH
2
)
6
NH CH
2
C
C
C
C
C
C
O H
H
H
O
H
C
C
C
C
C
C
C
O
H
CH
2
C O
CH
3
H
C
CH
3
H
H
C H
3
CH
3
H
H
OH
C
O
OH
m
(17)
Scheme 17.
Scheme 18.
However, the selectivity of Au-APT surfaces was much less
in serum-containing conditions. Au-g-POEGMA-APT surfaces with
POEGMA as an antifouling spacer, showed good selectivity for
Ramos cells in serumcontaining medium, and selectivity increased
with increasing surface roughness. The density of Ramos cells
was 6.6 times that of CEM cells on the roughest surface. It was
found that surfaces combining appropriate chemical composi-
tion and micro/nano roughness structures may be useful for cell
separation, including the isolation of cancer cells for diagnosis
[128].
Nevertheless recent developments have focused on the mussel-
inspired catechol chemistry for promoting adhesion of coatings
on organic and inorganic surfaces [169,170], making free rad-
ical scavenging nanoparticles [171] and modifying low surface
energy substrates [172]. It is interesting to note that the ortho-
dihydroxyphenyl group, referred to as a catechol group, is
assumed to be a key structural unit responsible for many different
functions of melanins [169].
Recent reports on mussel adhesive proteins postulate a sig-
nicant role of catecholic molecules like dopamine for surface
Fig. 8. Antifouling properties of Au-g-POEGMA-APT surfaces [128].
immobilizationandantifoulingsurfaces, wherethesubstrates were
dip-coated with dopamine based initiators followed by surface ini-
tiated polymerization and grafting of a variety of polymer brushes
like PEG, and other peptidomimetic polymers. Although gradual
growth and accumulation of biomass, commonly referred to as
biofouling, is a major problemaffecting surfaces that are in con-
tact with uids containing proteins, cells, and microorganisms.
Biofouling is also a serious problemin marine environments where
the increased drag due to biofouling can result in a 40% fuel
consumption increase in large commercial vessels with hull cor-
rosion and crevice formation as other costly detrimental effects.
Furthermore, leaching of active ingredients such as copper and
organic biocides from traditional antifouling coatings on marine
vessels has led to increasingly stringent regulation of these bio-
cidal coatings. Though the above-mentioned approaches which
involve dip-coating substrates with dopamine or dopamine initia-
tors (followed by growth of antifouling polymers in some cases)
can be a convenient antifouling approach for smaller surfaces
like ltration membranes and medical implants, they are less
applicable to larger surfaces like ships, buoys, and wave energy
converters [169173].
Cho et al. [173] have developed a synthetic approach to
prepare PMMA-b-PDA and PDA-b-PMMA-b-PDA tri-block copoly-
mers combining mussel-inspired catecholic oxidative chemistry
and ATRP (Fig. 9). First, a mono-functional (PMMA-Br) and a
bi-functional (Br-PMMA-Br) macroinitiators were synthetized by
ARGET ATRP (BIBB/CuBr
2
/ME
6
TREN/tin(II) 2-ethylhexanoate). In
the second step, copolymers had been synthetized by NI ATRP,
using a macroinitiator/CuBr/PMDETA initiation system.
These copolymers have improved solvent, mechanical and ther-
mal stability, as well as good fouling resistance (low protein
adsorption). Spin-cast thin lms of the copolymer were stable in
water and showed a sharp reduction (by up to 50%) in protein
adsorption compared to those of neat PMMA [173].
Fig. 9. Nucleophilic addition of PMMA radicals to PDA, combined with dopamine oxidative polymerization [173].
4.3. Antibacterial surface
Antimicrobial surfaces are widely used to prevent microbial
infection in a wide range of industrial, medical, community and
private settings. Antimicrobial surfaces have been successfully
prepared via immobilization of antimicrobial polymers onto var-
ious substrates. The biocidal polymer generally contained cationic
groups, such as alkyl pyridiniumor QA moieties. The interaction of
the cationic sites of quaternizedgroups withthe negativelycharged
membrane of bacteria has an adverse effect on the integrity of the
bacterial cell, as the QA groups can disrupt the plasma membrane
to cause the release of intracellular substances [174].
SI-ATRP has been used to impart antibacterial surfaces on tita-
nium[175177], lter paper [178], glass [155,178180], polyolen
[181,182], bers [183], gold [155,184187], silicon [135,179,184],
polymer microspheres [188], PVDF [189], polypropylene (PP) [181]
and SS [151]. In this case, the most commonly used substrates with
antibacterial properties are HEMA (formula 10b) [135,175,185],
DMAEMA (formula 10c) [178,179,181,183,188191], 2-(tert-
butylamino)ethyl methacrylate (TBAEMA) (formula 19a) [182],
2-(methacryloyloxy)ethyltrimethylammonium chloride (METAC)
(formula 19b) [151,186], 3-sulfopropylmethacrylate (SPM) (for-
mula19c) [187] andcarboxybetainemethacrylate(CBMA) (formula
19d) (Scheme 19) [155].
The original idea of preparing permanent, non-leaching antibac-
terial surfaces via ATRP was proposed by Matyjaszewskis group
[178]. Antimicrobial surfaces have alsobeenpreparedbyGuo-Dong
et al. [183]. As shown in Scheme 20, di-block copolymers with one
block of P(DMAEMA-c-GMA) and another of PPCPA (P(DMAEMA-c-
GMA)-b-PPCPA) were synthesized via ATRP, using EBIB as initiator.
Electrospinnning of P(DMAEMA-c-GMA)-b-PPCPA from a solu-
tion in THF and N,N-dimethylformamide (DMF) gave rise to
microbers with diameters in the range of 3001.3mm (Fig. 10)
[183].
The QA salts were generated via N-alkylation of tertiary
amine groups of the P(DMAEMA-c-GMA) block by the chloro-
aromatic compounds of the PPCPA block (or self-quaternization
of P(DMAEMA-c-GMA)-b-PPCPA). Combination of the hydropho-
bic interaction of the PPCPA and the electrostatic interaction of QA
salts fromthe self-quaternization of P(DMAEMA-c-GMA)-b-PPCPA
gives the resulting microbers a highantibacterial activity. Increas-
ing the PPCPA content of microbers can improve the antibacterial
efciency [183].
More recently, Gao et al. [176] have synthesized poly-
(N,N-dimethylacrylamide-c-N-(3-aminopropyl)-methacrylamide
hydrochloride) (P(DMA-c-APMA)) brushes on Ti surface by SI-ATRP
in aqueous conditions, in the presence of CuCl/CuCl
2
/HMTETA
(1,1,4,7,10,10-hexamethyltriethylenetetramine) catalyst complex
(Scheme 18).
To generate ATRP initiators groups on Ti surface it was neces-
sary to performmodication in two steps: initial functionalization
to generate amine groups (Scheme 21a and b) and hydroxyl
groups followed by modication with 2-chloropropionyl chloride
(CPC) (Scheme 21c and d). In the rst order, amine modi-
cation of acid-pretreated Ti deposited silicon wafer (Ti) with
3-aminopropyltriethoxylsilane (APTES) in dry toluene was per-
formed resulting in covalently bonded siloxane lms (Ti-NH
2
).
Primary amine functionalized Ti surface was further modied
using glycidol (GLY) to generate hydroxyl modiedsurface (Ti-OH).
ATRP-initiator modied surfaces were generated by treating Ti-
NH
2
or Ti-OHwithCPC, andthenwereusedintheSI-ATRP, toobtain
a P(DMA-c-APMA) brushes (Scheme 21e). Subsequently, cysteine
functionalized cationic antimicrobial peptide Tet-213 was conju-
gated to the copolymers brushes using a maleimidethiol addition
reaction after initial modication of the grafted chains using
3-maleimidopropionic acid N-hydroxysuccinimide ester (BMPS).
After which ME was added for 1 day to quench the remaining
maleimide groups in copolymer brush (Fig. 11) [176].
(19)
O CH
2
CH
2
NH
C H
2
C
CH
3
C O
C
CH
3
CH
3
CH
3
a)
O CH
2
CH
2
N
+
C H
2
C
CH
3
C O
CH
3
CH
3
CH
3
Cl
b)
S O
O
O
CH
2
O CH
2
CH
2
C H
2
C
CH
3
C O
c)
C O
O
O CH
2
CH
2
N
+
C H
2
C
CH
3
C O CH
3
CH
3
CH
2
CH
2
d)
Scheme 19.
(20)
C
O
C
CH
3
CH
3
Br O CH
2
C H
3
O
C H
2
C
CH
3
C O
CH
2
CH
2
N
C H
3
CH
3
O
C H
2
C
CH
3
C O
CH
2
CH
CH
2
O
C
O
O C
CH
3
CH
3
CH
3
CH
2
CH
2
C CH
2
n
C Br
CH
3
O
C O
CH
2
CH
2
N
C H
3
CH
3
m
O
C O
CH
2
CH
CH
2
O
CH
3
O
C H
2
CH
C O
Cl Cl
Cl
Cl
Cl
C
O
O C
CH
3
CH
3
CH
3
CH
2
CH
2
C CH
2
n
C
CH
3
O
C O
CH
2
CH
2
N
C H
3
CH
3
m
O
C O
CH
2
CH
CH
2
O
CH
3
CH
2
C
O
C O
CH
3
Br
m
Cl Cl
Cl
Cl
Cl
+
a)
EBB
GMA
b)
CuBr/PMDETA
+
CuBr/PMDETA
DMAEMA P(DMAEMA-c-GMA)
P(DMAEMA-c-GMA) +
PCPA P(DMAEMA-c-GMA)-b-PPCPA
Scheme 20.
The peptide density (peptides/nm
2
) on the surface varied with
the initial composition of the copolymer brushes. Lowgraft density
brushes are more adhesive than high graft density brushes even
though the high graft density brush has more peptide surface den-
sity. A surface having low hydrophobic adhesion showed better
antimicrobial properties [176,177].
Also the SI-eATRP method has been widely used to prepare
antibacterial surfaces. For example Li et al. [185] have synthe-
sized PHEMA brushes on Au surface (Au-g-PHEMA) froma MUBIB
SAM immobilized on gold substrate (Au-SAM), in the presence of
CuCl
2
/Bpy catalyst complex. More recently Li et al. [186] have pre-
pared PMETAC brushes on Au surface (Au-g-PMETAC), also froma
Au-SAM, in the presence of CuCl
2
/Bpy catalyst complex.
These two types of polyelectrolyte brushes fabricated through
SI-eATRP and traced by in situ AFM demonstrate effective way
to simultaneously investigate the growth activities and morphol-
ogy of a specic monomer under a relaxed environment. The
polymerization can be switched on and off articially by adjus-
ting the ratio of Cu(II)/Cu(I) electrochemically, and is superior
to the conventional method [186]. It allows polymer brushes to
grow in the presence of ambient air and the monomer solu-
tion can be reused for several times, which is very promising for
the polymerization of specialty monomers and for the growth of
biocompatible, protein-resistant polymer brushes on non-planar
substrates with complex shapes [185]. Besides, surfaces modied
with polyelectrolyte brushes have potential applications in areas
such as biosensors, smart coatings [186].
4.4. Stimuli-responsive surface (micelles)
Stimuli-responsive polymer brushes have played an important
role in biomedical applications, such as thermo-responsive sub-
strates for cell culture, biomolecular diagnostics/biosensors and
controlled drug delivery [192]. Polymer systems can be modulated
by physical stimuli (such as temperature, pressure, electric or mag-
netic elds) and chemical stimuli (such as pH, ionic strength and
chemical agents) [193].
Different stimuli-responsive polymer brushes have been pre-
pared via ATRP to produce temperature-responsive [194219]
and pH-responsive surfaces [207,208,220224]. Responsive block
Fig. 10. SEMsurface images of microbers electrospun fromP(DMAEMA-c-GMA)-b-PPCPA at a concentration of about 20wt% (a), and microbers fromP(DMAEMA-c-GMA)-
b-PPCPA with an electrospinning concentration of 15wt% (b) [183].
CH
2
O Si
O
O
CH
2
CH
2
CH
2
CH
2
CH
3
CH
3
CH
2
NH
2
CH
3
OH
C
7
H
8
CH
3
OH + HCl
OH
OH
H
2
SO
4
O H
2
Si
O
O
CH
2
CH
3
CH
3
CH
2
CH
2
NH
2
O
Cl C C
O
Cl
CH
3
Si
O
O
CH
2
CH
3
CH
3
CH
2
CH
2
NH O Cl C C
O
CH
3
CH CH
OH
CH
O
Si
O
O
CH
2
CH
3
CH
3
O CH
2
CH
2
N
CH
CH
OH
OH
CH
2
HO
CH
2
HO
Si
O
O
CH
2
CH
3
CH
3
O CH
2
CH
2
N
CH CH
2
O Cl C C
O
CH
3
Cl C C
O
CH
3
Cl C C
CH
3
O
a)
+
b)
Ti-OH Ti-NH APTES
Ti Ti-OH
d)
c)
2
Ti-NH2 +
CPC
Ti-N-Cl
TEA
Ti-NH2 +
GLY
Ti-OH
DMF
Ti-O-Cl
CPC
CH
2
CH
C O
N
C H
3
CH
3
CH
2
CH
C O
NH
CH
2
CH
2
CH
2
NH
3
Cl
CH
2
CH
C O
N
C H
3
CH
3
O CH
2
CH
C O
NH
CH
2
CH
2
CH
2
NH
3
Cl
n m
P(DMA-c-APMA)
e)
+
Ti-N-Cl
Ti-O-Cl
DMA
+
APMA
+
CuCl/CuCl /HMTETA
2
+
(21)
Scheme 21.
Fig. 11. Representation of Ti substrate grafted with copolymer brush (a), thickness increase after the conjugation of maleimide linker (b), and thickness increase after peptide
conjugation followed by ME quenching (c) [176].
(22)
NH
C H
2
CH
C O
CH
C H
3
CH
3
a)
OH
C H
2
CH
C O
b)
Scheme 22.
copolymers typically contain a hydrophilic block and a smart
block that can be transformed from hydrophilic to hydrophobic
characteristics viathemanipulationof external environmental con-
ditions [201].
SI-ATRP has been used to impart stimuli-responsive surfaces
on silicon [196199], gold [200], glass [194] and tissue culture
polystyrene (TCPS) [215]. Moreover, the most commonly used sub-
strates with stimuli-responsive properties are NIPAM (formula
22a) [192,194200,202204,206,210213,215219], AA (formula
22b) [221,224], OEGMA (formula 10a) [192,201,205,206,216] and
DMAEMA (formula 10c) (Scheme 22) [207,208,210,220,223].
One popular thermo-responsive polymer poly(N-
isopropylacrylamide) (PNIPAM) has been widely studied
because its LCST is close to the body physiological temperature
[201]. PNIPAMexhibits a LCST of about 32
Cinanaqueous medium
[202]. It assumes a randomcoil structure (hydrophilic state) below
the LCST and a collapsed globular structure (hydrophobic state)
above the LCST due to rapid, reversible chain dehydration and
aggregation [192]. Because of this unique property, well-dened
PNIPAM brushes have been widely used in the preparation of
stimuli-responsive surfaces for controlling drug delivery systems
[196,200,209,210,212,216,217] and cell adhesion/detachment
[194,195,197,211,212], as well as killing and release of bacteria in
response to changes in temperature [219].
Examples of thermo-responsive PNIPAM block copolymers
for controlling drug delivery systems are poly(N-isopropyl-
acrylamide)-b-poly[(R)-3-hydroxybutyrate]-b-poly(N-isopropyl-
acrylamide) (PNIPAM-b-PHB-b-PNIPAM) (formula 23) [204],
poly(N-isopropylacrylamide)-b-poly(3-caprolactone)-b-poly(N-
isopropylacrylamide) (PNIPAM-b-PCL-b-PNIPAM) (formula
24) [203] and poly(N-isopropylacrylamide-co-N-hydroxy-
methylacrylamide)-b-poly(ethylene glycol)-b-poly(N-isopropyl-
acrylamide-co-N-hydroxymethylacrylamide) (P(NIPAM-c-HMAM)
(25)
CH
2
CH
C
NH
CH
C H
3
CH
3
CH
2
CH
C
Br
a
NH
CH
2
OH
CH
2
CH
2
O CH
2
CH
C
NH
CH
CH
3
C H
3
O
CH
2
CH
C
Br
a
NH
CH
2
O
OH
n
O O
Scheme 25.
(26)
CH
2
C
CH
3
Br C
O
O C
CH
3
CH
3
CH
3
CH
2
CH
2
CH CH
2 x
CH
O
C O
(CH
2
)
2
O
(CH
2
)
2
O
C O
O
CH
3
y
CH
2
CH
2
O CH
3 n
n = 8/9
Scheme 26.
-b-PEO-b-P(NIPAM-c-HMAM)) (formula 25) (Schemes 2325)
[216].
However, there are limited commercial applications using PNI-
PAMfor biomedical applications as NIPAMmonomer is suspected
to be carcinogenic [201].
Therefore, biocompatible thermal responsive polymers com-
posed of POEGMA have attracted increasing attention, since ran-
domcopolymers of poly(2-(2-methoxyethoxy)ethyl methacrylate-
co-oligo(ethylene glycol) methacrylate) P(MEO
2
MA-c-OEGMA)
prepared via ATRP was shown to exhibit sharp thermal transitions
that are similar to PNIPAM(formula 26) (Scheme 26) [205].
It was found that the LCSTs of POEGMA based copolymers can
be tuned to the physiological temperature by varying the feed ratio
of monomers. Also their LCSTs are mildly sensitive to salt concen-
tration, ionic strength and in-vitro cell tests of several POEGMA
analogs showed excellent biocompatibility. This kind of polymeric
micelles have potential applications for drug delivery and other
biological applications [201].
(23)
C
O
O CH
2
CH
2
C
O
O CH
2
CH C
O
O C
CH
3
m
C
CH
3
CH
3
CH
2
CH
C O
Br
x
NH
CH
C H
3
CH
3
CH
3
CH
3
CH
2
CH
C
Br
x
NH
CH
CH
3
C H
3
O
Scheme 23.
(24)
C
O
(CH
2
)
5
O
z
O (CH
2
)
2
O (CH
2
)
2
C
O
O (CH
2
)
5
C
O
O C
z
CH
3
CH
3
CH
2
CH
C
Br
x
NH
CH
CH
3
C H
3
O
C
O
C
CH
3
CH
3
CH
2
CH
C O
Br
x
NH
CH
C H
3
CH
3
Scheme 24.
(27)
CH C O
CH
3
O
CH
2
CH
2
O
n
C H
3
CH
2
CH
C
NH
CH
CH
3
C H
3
O
CH
2
CH
C
O
CH
2
q
O
C
H
C H
N N
N
p
CH
2
CH
2
O
CH
2
C
O
C
CH
3
C O
CH
2
CH
3
CH
3
k
CH
2
CH
2
N
CH
3
C H
3
pH-responsive
thermo-responsive
Scheme 27.
Meanwhile, the most extensively studied pH-responsive poly-
mers are PDMAEMA [207,208,210,220,223] and poly(acrylic acid)
(PAA) [221].
PDMAEMA is able to function as the pH-responsive component
as it has a nitrogen moiety, which can be protonated by lowering
the pHof the solution [220], and shows pH-dependent LCST behav-
ior [207] and upper critical solution temperature (UCST) behavior
at low temperatures in the presence of multivalent counter ions
[208]. It has the potential applications in the elds of environmen-
tal protection, drug delivery systems, sensors, paints, membranes,
antibacterial materials and anticancer activity [223].
Also, PAA has pH-stimuli responsive to the various organs and
tissues of the body and the stimuli responsive can be tuned by the
changing the type and content of other composition in polymer.
PAA can be widely used as a pH-responsive material to prepare a
pH-responsive controlled release applied in drug delivery system
[221].
Nevertheless recent developments have focused on the fab-
rication of doubly responsive micelles [225233]. For example
Zhang et al. [225] have prepared block-brush copolymer of PEG-
b-P(NIPAM-g-DMAEMA) (formula 27), which showed temperature
and pH response(Scheme 27).
Meanwhile Loh [228] has synthesized a doubly responsive
copolymer based on PDMAEMA, and PPPGMA by ATRP technique
(formula 28) (Scheme 28).
These amphiphilic copolymers formed micelles in solution, and
their morphologies can be controlled by temperature and pHof the
external environment (Fig. 12) [228].
At elevated temperatures and low pH, micelles were formed
withthe hydrophobic PPPGMAcore andthe hydrophilic PDMAEMA
corona. To reverse the morphology of the micelle, the tempera-
ture is lowered and the pH raised, resulting in the formation of
micelles with the hydrophobic PDMAEMAcore and the hydrophilic
PPPGMA corona. These copolymers were nontoxic to cells and can
be use as a multi-responsive carrier vehicle for the delivery of drugs
and other therapeutics to the body [228].
More recently, Ruiz et al. [229] describe the preparation of
functional polymer surfaces, starting from blends of PS and an
amphiphilic block copolymer PS-b-PAA. The micelles formed in
bulk are able to migrate towards the interface upon water vapor
annealing, thus formingspherical nanodomains withthecarboxylic
groups of PAAexposedto the polymer/humidair interface. The PAA
nanodomains were complexated with PVP, PNIPAM and poly(N-
tert-butylacrylamide) (PNTBAM) via hydrogen bond interactions
(formula 29) (Scheme 29).
PNIPAM/PAA and PVP/PAA complexed surfaces are reversible,
that is, it is possible to form and disrupt both complexes by
simply modifying pH. Similarly, the reversibility of PNTBAM/PAA
complexed surfaces is possible through a change of solvent from
propanol to methanol (Fig. 13) [229].
Authors expect for this systempotential applications indifferent
elds including selective adsorption purposes, biomedical applica-
tions, or drug release frompolymer surfaces [229].
In recent years, the increasing need for smartness in biomedi-
cal and engineering materials has generated a growing interest for
synthetic polymers used as matrices for drug-eluting stent (DES)
coatings [234243].
Device-based drug delivery is highly dependent on polymeric
materials to serve as coatings and matrices (SS) to release the
(28)
O
C
CH
3
C O
CH
2
CH CH
2
Br
x
CH
2
CH
2
N
C H
3
CH
3
C
CH
3
CH
3
C O
O
C
2
H
5
C
O
O CH
CH
3
CH
2
OH
n
y
n = 5
pH-responsive thermo-responsive
Scheme 28.
Fig. 12. Diagramto illustrate the reversible micelle concept [228].
therapeutic in a controlled fashion. Important consideration for
polymeric drug delivery coatings is the ability to modulate the
release of the therapeutic to allow for a range of delivery rates
to meet the clinical requirements of the intended treatment. One
effective approach to tailoring the release rate of a drug from a
polymer is through changes to the polarity of the coating to affect
the hydrophilic/hydrophobic balance of the matrix. This can allow
control of both the ingress of the aqueous environment to dissolve
and remove drug as well as the egress of the drug by diffusion
through the coating [234].
More recently Shaulov et al. [235] describe possible method
for improving the durability and adhesion of drug-in-polymer
coatings of SS surfaces involves modication of the stent sur-
face by the three-step process (Fig. 14). In the rst step,
Scheme 29.
Fig. 13. Scheme of the formation and disruption of the pH and solvent responsive polymers [229].
Fig. 14. Subsequent steps of the stents coating process [235].
Fig. 15. Strategy for preparing MIPs [247].
4-(2-bromoethyl)benzenediazonium tetrauoroborate was elec-
trografted onto a SS stent. In the second step, methyl methacrylate
was polymerized onto the grafted surface by atom-transfer radical
polymerization. Thelast stepinvolvedspraycoatingof themodied
stents with a drug-in-polymer matrix [poly(n-butyl methacrylate)
(PBMA)/poly(ethylene-co-vinyl acetate) (PEVA) +PTX] or with an
additional layer of PBMA (double-layer coating) to receive DESs.
Bare controls showed greater cracking and delamination of the
coating than did the two-step modied stents after incubation
under physiological (37
C) and accelerated (60
C) conditions. PTX
controlled release from the modied SS DESs was moderate com-
pared with that of nontreated samples [235].
Richardet al. [234] have synthesizedelastomeric acrylate-based
block copolymers by ATRP, for potential applications as drug deliv-
ery matrices for the controlled release of PTX fromcoronary stents.
These multiblock copolymers were consisted of immiscible blocks
that resulted in unique nanophase-separated materials PBA or
poly(lauryl acrylate) (PLA) soft blocks and hard blocks composed
of PMMA, poly(isobornyl acrylate) (PIBA) or PS.
In vitro PTX release kinetics from coronary stents coated with
these copolymers showed an early burst followed by sustained
release behavior, which permitted the elution of the majority of
the PTX over a 10-day time period. It was stated that neither the
nature of the polyacrylate (n-butyl or lauryl) nor that of the hard
block appeared to affect the release kinetics of PTX at a loading of
25% drug by weight, whereas some effects were observed at lower
drug loading levels [234].
Nevertheless recent developments have focused especially on
the dense polymeric brushes covalently attached to the surface
of gold [244], glass [245], mica [246] or oxidized silicon wafer
[247249] by SI-ATRP. In many cases, these polymeric brushes can
be serve as effective etching barriers for microlithographic appli-
cation, yield excellent mechanical and chemical protection, alter
the chemical and electrical interface properties of the underly-
ing substrates, and provide newroutes to functionalize surface for
molecular recognition and sensor device. Different fromthe tradi-
tional grafting, the preparation of polymeric brushes grafted from
the surface includes a two-step procedure, the self-assembly of
initiator, and the controlled polymerization [248].
Yildirimet al. [247] describe the preparation of 2-DMIP and NIP
lms with recognition properties on a silicon substrate using myo-
globin (Mb) as the template, HEMA as the functional monomer and
EGDMA as the cross-linking agent with a SI-ATRP method (Fig. 15).
Silicon wafers were functionalized with 3-
bromopropyltrimethoxysilane (BPTS). Afterwards, 2-D MIP
and NIP lms were grown from SAM on silicon wafers using
SI-ATRP method (CuBr
2
/Bpy/EBIB) [247].
The MIP lms exhibited higher rebinding capacity than the NIP
lms at all solution concentrations of Mb. From AFM measure-
ments, both the MIP and NIP surfaces appear to be macroscopically
and microscopically smooth; they have similar roughness values
and morphologies (Fig. 16). The controllable nature of ATRP allows
the growth of uniformMIP lms with adjustable thickness [247].
MIPs have an application in diagnostic analysis, because it can
be served as antibodies able to replace their natural counterparts.
More recently Turan et al. [248] describe the preparation of
homogeneous and dense tethered PNIPAMbrushes with hydroxyl
end-group on the silicon wafer surface in the presence of ME chain
transfer agent by combining the self-assembly of initiator and the
SI-ATRP technique. The initiator-immobilized substrate, was pre-
pared by the esterication of hydroxyl groups on silicon wafer
with 2-bromopropionyl bromide (2-BPB); followed by the ATRP
of NIPAM using a catalyst system, that is, CuBr/Bpy and a chain
transfer agent, that is, ME (Scheme 30).
The ME chain transfer agent was not only used to form the
hydroxyl-terminated PNIPAM brushes but also control over the
polymer molecular weight, grafting parameters, wettability, and
surface morphology (Fig. 17) [248].
The introductionof hydroxyl groups intopolymer chains as end-
group increased the hydrophilicity of PNIPAMbrushes. Meanwhile,
the surface roughness of the polymer brush with higher hydroxyl
content is less thanthe size of the free polymer chain, indicatingrel-
atively homogeneous and uniform surfaces. Higher concentration
of ME chain transfer agent and higher grafting density resulted in a
slightly better dened domain morphology of the PNIPAMbrushes
[248].
Recently, the synthesis of stimuli-responsive surfaces via
surface-initiated SET-LRP which include homopolymer, block
copolymer and polymer brushes has garnered more and more
attention [75,78,80,82,86,87].
Turan and Caykara [75,78,80,82] have focused on surface-
initiated SET-LRP of NIPAM from silicon wafer modied with an
initiator layer composed of 2-BPB fragments. Polymerization was
carried out by Cu(0) generated from the disproportionation of
CuBr/Bpy in the presence of 2-mercaptoethylamine [78] or cys-
teamine [80,82] as chain transfer agent.
Demirci et al. [87] describe the synthesis of stimuli-responsive
PNIPAM-b-PVBA di-block copolymer brushes on hydrogen termi-
nated silicon wafer substrate via combination of click reaction,
SET-LRP, and reversible addition-fragmentation chain transfer
polymerization (RAFT). Azide-terminated PNIPAM brushes were
obtained by SET-LRP followed by reaction with sodium azide. A
click reaction was utilized to exchange the azide end group of a
PNIPAMbrushes to forma surface-immobilized macro-RAFT agent,
which was successfully chain extended via RAFT polymerization to
produce copolymer brushes.
The PNIPAM-b-PVBA brushes demonstrate stimuli-responsive
behavior with respect to pH and temperature. The swollen brush
thickness of copolymer brushes increases with increasing pH, and
decreases with increasing temperature. These results can provide
guidance for the design of smart materials based on these copoly-
mer brushes [87].
More recently, [86] surface-initiated SET-LRP was used to syn-
thesize on silicon surfaces polymer brush containing NIPAM and
adamantyl acrylate (ADA) using Cu(I)Cl/Me
6
-TREN as precursor
catalyst. The hydrophilic and bioactive molecule -cyclodextrin-
(mannose)7 (CDm) was synthesized and complexed with adaman-
tane via host-guest interaction (Scheme 31).
Experimental and molecular structure analysis showed that
ADA at certain content together with CDmhas the greatest impact
on wettability and thermo-responsive property of surface. The
surface wettability increased with the increase of ADA feed ratio
(<4.76%). Furthermore, when ADA content was in a mediumrange
(3.454.76%), both LCST and the hydrophilicity of copolymer sur-
faces after complexation with CDmexhibited an increase [86].
4.5. Hydrogels (tissue engineering scaffolds)
Polymeric scaffolds play an important role in tissue engi-
neering. They can mimic the roles of extra cellular matrixes
found in tissues and regulating the function of cells. To function
Fig. 16. Topography of AFM images in ambient conditions, surface cross-section analysis, and static contact angle for BPTS layer (root-mean square (rms) rough-
ness =0.40.1nm) (a), NIP surface (rms roughness =2.90.1nm) (b) and MIP surface (rms roughness =3.10.2nm) [247].
properly in the body and promote new tissue formation, poly-
mers for tissue engineering must be biocompatible anddegradable,
while still maintaining certain physical properties helpful to cell
growth [250].
One challenge is to create biodegradable polymeric materials
with appropriate mechanical properties that can be modied to
incorporate biological activity [251]. These polymers canbe natural
materials such as collagen gels and carbohydrate-based hydrogels.
Alternatively, polymer scaffolds can be made fromsynthetic mate-
rials, andcombinations of natural andsynthetic materials, that offer
the greatest range of physical properties and functionalities, e.g.
physically crosslinked copolymer hydrogels [70].
Hydrogels are crosslinked polymer network structures that
have the ability to absorb large amounts of water without dis-
solving. Because of their elasticity and soft, tissue-like physical
properties, they have the hydrodynamic properties of cells in
many ways. Hydrogels alsominimize the frictional irritationwithin
the surrounding tissue upon implantation [252]. The high mobil-
ity of macromolecular chains at their surface and their surface
hydrophilicity contribute to improved biocompatibility [253]. Due
Scheme 30.
Fig. 17. Topography of AFM images in ambient conditions, surface cross section analysis, and static contact angle for hydroxlated silicon (rms roughness =0.412nm)
(a), initiator monolayer (rms roughness =0.624nm) (b), hydroxyl-terminated PNIPAM brushes synthesized in 0.07M (rms roughness =4.717nm) (c) and 0.112M (rms
roughness =2.212nm) (d) ME solutions [248].
to these properties, hydrogels nd valuable applications for soft
tissue substitution [254256], scaffolds for tissue engineering
[257259], contact lenses [260,261], catheter coatings [262,263],
cells encapsulation [264,265], drug delivery vehicles [266268],
wound dressing [269], articial organs [270] and biosensors [271].
Although hydrogels are being increasingly used in biomedical
devices, their poor mechanical properties are still major prob-
lems for biomedical applications. The usual method for improving
the mechanical properties of hydrogels relies on the introduc-
tion and variation of crosslinkers. However, chemically crosslinked
hydrogels cannot be reshaped because the hydrogels are no longer
soluble in organic solvents. Because unreacted crosslinker residues
from the hydrogels are no longer soluble in aqueous extraction
media, the removal of residue from the hydrogels is also prob-
lematic. Moreover, the postprocess modication of chemically
crosslinked hydrogels is not possible because of the insolubility of
the chemically crosslinked hydrogels in most solvents. The physi-
cally crosslinked hydrogels in this regard are benecial for ease of
fabrication and postprocess modications [272].
Due to the excellent mechanical properties of PU, hydrogels
based on their chemistry are appealing for biomedical applications.
PU based hydrogels can form strongly hydrogen bonded struc-
tures, allowing linear polymer systems to be designed with tunable
swelling and mechanical properties [273]. However, the chemos-
electivity to synthesize PU hydrogels is limited since most of the
available PU soft segments are hydrophobic. The CRP methods
allowed the design of tailored hydrogels with a desired molecular
weight distribution and composition [274].
Oneof theCRPmethods that couldemployPUis themacroinifer-
ter technique. It has been widely used to synthesis various
physically crosslinked copolymer hydrogels: PU-b-PAA (formula
32) [275], polyurethane-b-itaconic acid (PU-b-I) (formula 33)
Scheme 31.
S
N H
2
O
x
N
C
2
H
5
S
S N
S
C
2
H
5
O
N O N
n
N O
O
H O
H H
O
O
N
O
H
(CH
2
)
4
m
(32)
Scheme 32.
CH
2
C CH
2
C
C
C
OH
OH
O N (CH
2
)
4
O N
n
N O
O
H O
H H
O
N
O
H
m
C
O
O
x
(33)
Scheme 33.
C CH
2
N
C O N (CH
2
)
4
O N
n
N O
O
H O
H H
O
N
O
H
m
C
x
O
(34)
Scheme 34.
C CH
2
C
C
O
O
N (CH
2
)
4
O N
n
N O
O
H O
H H
O
N
O
H
m
C
O
x
CH
2
CHOH
CH
2
OH
CH
3
(35)
Scheme 35.
Fig. 18. PEG-armed Ru(II)-star polymers [280].
[276], PU-b-PVP (formula 34) [277] PU-b-PGMA (formula 35)
(Schemes 3235) [278].
These hydrogels showed interesting properties (excellent
hydrophilicity and swelling behavior higher swelling at both
low and high pH than at a neutral pH, and low platelet adhe-
sion, lowbrinogen, andhigher albuminadsorptions) whichmakes
themideal candidates for coating blood-contacting devices such as
catheters for hemodialysis, drug delivery, and scaffolds for tissue
engineering [275278].
4.6. Microgel-core star polymers
Macromolecular or polymeric capsules comprisingwell-dened
and spatially isolated cavities are now key materials for delivery
(drug, gene, and imaging agents), catalyst scaffolds, microreactors,
and biomedical applications, among others [279]. Polymeric scaf-
folds andcapsules, for example microgel-core star polymers, canbe
designedtomeet specic objectives andapplications, sophisticated
functions often require complex architectures and thus impose
cumbersome and multistep preparation. In particular, given a large
number of functionalities to be implanted into their arms, cores,
and surface (arm ends), these polymers are expected to provide
unique and novel functionalized polymers of interesting spatial
shape and multiple functions [280].
Microgel-core star polymers [281290] a unique class in
nanogels, carry nanoscale cross-linked central cores (1030nm
in diameter) that are covered by multiple linear polymeric arms
with which, despite the gel core, the entire molecules are totally
soluble incommonsolvents. LRP is especially suitable for microgel-
core star polymers because it proceeds via the neutral propagating
species to facilely afford direct functionalization, either on arms or
cores or both, with the use of functional monomers and/or linking
agents without protectionand deprotection[106,291,292]. Various
core-functionalized star polymers have been prepared by the arm-
linking reaction with functional linking agents and/or monomers
(cores) inruthenium-catalyzedLRP [283286,293295]. The core
functional groups including amide or hydroxyl groups, peru-
oroalkanes, phosphine ligands, and metals are introduced and
condensed into their cores to perform unique molecular recogni-
tion and catalysis [296].
Recent developments in this eld have focused on the
arm functionalization of the ruthenium-bearing star polymers
[280,296300]. For example Terashima et al. [280] have reported
a novel synthetic pathway (Fig. 18) to PEG-armed star polymers
with Ru(II)-enclosed microgel cores (Ru(II)-PEG star) via one-pot
Fig. 19. PMMA-armed Ru(II)-star polymers [289].
transformation of polymerization catalysts into amphiphilic,
homogeneous star polymer catalysts. ThelivingPEGMAarms were
subsequently cross-linked with a dimethacrylate as a linking agent
in the presence of a phosphine-ligand functionalized styrene, to
produce the PEG-armed star polymers with Ru(II)-encapsulated
microgel-core.
The PEG-armedstar polymers were alsofoundtobe amphiphilic
(soluble in both alcohols and water) and thermosensitive (UCST
near 30
C in 2-propanol).
More recently, Terashima et al. [290] were synthesized similar
PEG-armed star polymers with Ru(II)-encapsulated microgel-core,
except that in this case star catalysts were sequential linking with
ethylene glycol dimethacrylate and diphenylphosphinostyrene.
Ru(II)-PEG star showed high catalyst recyclability, independent
of the substrate species. These features most likely arise from its
unique reaction space, which consists of a ruthenium-embedded,
hydrophobic microgel core surrounded by amphiphilic and polar
PEGMA arms.
Moreover Terashima et al. [289,297] have prepared another
star polymers containing ruthenium complex in the core by
ruthenium-catalyzed LRP, where the metal catalysts were directly
encapsulated on linking reactions of living PMMA in the presence
of EGDMA as a linker and diphenyl-4-styrylphosphine as a ligand
incorporated in the core (Fig. 19).
Meanwhile Fukae et al. [296] were synthesized cation-
condensed microgel-core star polymers with PEG-based arms
were designed as unimolecular polycationic nanocapsules (hosts)
to encapsulate and stimuli-responsively release hydrophilic and
anionic dyes (guests) in water (Fig. 20).
Typically, a cation-condensed star polymer (core cations:
670/star) was directly synthesized in high yield (>90%) by the
Fig. 20. Encapsulationandreleaseof hydrophilic dyes of cation-condensedmicrogel
star polymers in water [296].
linking reaction of a PEG macroinitiator with a quaternary ammo-
nium cation-carrying linking agent in ruthenium-catalyzed LRP.
Owing to the locally high concentration of quaternary ammonium
cations inthecore, thestar polymers affordedefcient andversatile
encapsulation of various dyes carrying sodiumsulfonate in water.
The efcient dye encapsulation is due to the high concentration of
quaternary ammonium cations in the core. Additionally, stimuli-
responsive release of dyes from cation-condensed star polymers
was successfully achieved via ion exchange with NaCl aqueous
solution. Cation-condensed star polymers would be useful as ver-
satile delivery vessels, contributing to a wide variety of biomedical
applications [296].
5. Comercial applications of copolymers
In the early years of ATRP development, the expected fast and
broad development of ATRP for the production of large volume of
materials was frustrated by the large amounts of catalyst complex
needed to control the polymerization. For both economical and
environmental aspects, the level of potentially hazardous catalyst
in the material had to be strongly decreased to bring ATRP poly-
mers into the marketplace. ATRP catalyzed by copper complexes
has been by far the most studied and developed industrially [301].
The promotion of ATRP towards industry began through the
ATRP Consortium founded by Prof. K. Matyjaszewski at Carnegie
Mellon University (CMU) of Pittsburgh, PA, USA. It lasted for ve
years (19962000) and gave rise to several U. S. patents issued
and licenses signed with industrial partners [302]. In 2006, ATRP
formed the basis for a CMU spin-off company called ATRP Solutions
that uses the technology to develop novel materials for evaluation
by their customers in their targeted markets [303]. Since 2003,
ATRP has been licensed to 8 of the over 40 corporations funding
the research at CMU (Kaneka, PPG, Dionex, Ciba, Mitsubishi, WEP,
ATRP Solutions, and Encapson). Licensees around the world have
begun commercial production of specialty polymers [304].
With the aid of numerous reports in literature, copolymers with
precisely controlled complex architectures have been commer-
cially produced by ATRP in U. S., Japan, and Europe since 2002,
and nd applications among other as components of coatings
[304], adhesives [305], polar thermoplastic elastomers [306308],
hydrogels [254,255,257,258,260262,264271], surface modiers
[304,309], sealants [305], blend compatibilizers [310,311], wet-
ting agents [310], surfactants [312316] and pigment dispersants
[317319]. In the latter example, they were used for coating com-
pounds, prints, images, inks or lacquers, andother disperse systems
[320].
In this case, for optimization of the costperformance relation-
ship some structural imperfections can be tolerated. They may
include missing arms in star polymers, loss of functionality, addi-
tional branching, and polymers with broader MWD. Sometimes
higher DI of chains may not only facilitate processing but also
provideaccess tomaterials withnewnanostructuredmorphologies
[15].
(36)
CH
3
O CH CH
2
C O
O
n
R
C
O
CH CH
2
O C
O
CH C H
2
R = H or
Scheme 36.
(37)
CH
3
Si CH CH
2
C O
O
n
R
CH
3
Si C H
3
O
O
CH
3
CH
3
O
O C H
3
C H
3
R = H or
Scheme 37.
One of the earliest industrial adopters of ATRP for large-scale
polymer production was Kaneka. Kaneka XMAP range of products
include several commercial reactive telechelic materials, for exam-
ples moisture-curable and addition-curable PBAdirected at sealant
andadhesive markets [301]. The most commonKaneka XMAPpoly-
mers arepolyacrylates typeC(free-radical inducedcuringbymeans
of UV or heat) (formula 36) and type S (moisture curable sealant)
(formula 37) (Schemes 36 and 37).
These polymers exhibit lowMWD (1.11.3 for most grades) and
high end-functionality. A range of molecular weights and main
chain compositions is available [321]. The main advantages over
current products are excellent performances in weatherability,
high heat, oil and ultraviolet resistance. One of the advantages that
accrue from use of environmentally stable materials is their non-
staining characteristics [305]. The benets are seen in the lack of
surface contamination on articial marble attached to the exte-
rior of buildings by sealants (Kaneka XMAP polyacrylates type C)
(Fig. 21a and b) prepared using ATRP (a perfect example is the
comparison of Fig. 22a with Fig. 22b and c) [321].
Furthermore these polymers have been developed for a vari-
ety of applications such as sealants, adhesives, coatings, gaskets
and pottings. Some examples of projected applications are glaz-
ing sealants for TiO
2
-coated glasses, oil resistant gaskets, elastic
adhesives, liquid injection molding, coatings, oil resistant linings,
exible foams as well as pressure sensitive adhesives [301].
Another active licensees corporation with a strong patent cov-
erage is PPG Industries. PPG explored ATRP as a means to design
lowDI, functional polymer additives of various controlled architec-
tures (including block, gradient, graft, comb and star copolymers)
as components for various coatings applications. ATRP copolymer
materials that were evaluated include for example TiO
2
-treated
glass of the self-cleaning properties for use inofces andresidential
buildings [304].
Furthermore, ATRP provides many advantages in modica-
tion of surfaces with thin polymer lms, which can be used
to tailor the surface properties such as hydrophilicity/phobicity,
Fig. 21. Examples of glazing sealant for self cleaning glass in different buildings [322].
Fig. 22. Pictures of tiles attached with acrylate-based sealant prepared by ATRP (a), silicone-based sealant (b) and both KANEKA XMAP PBA and PDMS sealants showing
effect of contamination after exposure for 4 years [322].
(bio)-compatibility, adhesion, adsorption, corrosionresistance, and
friction. The surface properties can also be tuned by tethering block
copolymers, where the composition and size of each polymer seg-
ment affect the morphology and behavior of the polymer brushes
[323].
Moreover, copolymers prepared by ATRP were already suc-
cessfully used for drug delivery [107,324337] and for tissue
engineering applications [107,338340].
Thus, ATRP has already been employed in industry, and it
can be expected that in the near future it will surface as one
of the processes of choice for large-scale production of specialty
polymers.
6. Summary
As has been shown for use ATRP methods in the synthesis of
newtypes of polymer materials it is necessary to knowthe mecha-
nisms of polymer chain growth process described in the literature.
Therefore, the major attention was paid to these issues in this
work, however extensively describedinthe literature kinetic issues
were limitedhere, andfocusedmore to preparative andapplication
issues.
This Reviewaims to provide an overviewof selected but repre-
sentative recent developments, trends, and emerging applications
of functional block copolymers obtained by using a wide range of
ATRP methods.
New ATRP procedures that utilize ppm amounts of Cu in the
presence of RA are more environmentally benign than earlier ATRP
processes. Signicant progress has been made in ARGET ATRP
technique using trace amounts of catalysts. If high chain end func-
tionality is required, polymerization could be stopped at partial
monomer conversion and monomer recovered.
The present review summarizes recent research activities in
ATRP for copolymers with particular emphasis on coatings appli-
cations. The highly robust and exible ATRP techniques are
particularly suited for the preparation of protective coatings with
increased hydrophobicity, functional bioactive surfaces, includ-
ing antifouling and antibacterial surfaces. In addition to bioactive
surfaces, the preparation of functional biomaterials in the forms
of stimuli-responsive micelle delivery systems and hydrogels has
also been conveniently accomplished by ATRP and macroinifer-
ter CRP techniques. Besides the above coating applications, other
applications such as microgel-core star polymers obtained by
ruthenium-catalyzed LRP, are also worth mentioning.
It is possible to notice that the greater attention, up till now,
is returned to the modication of acrylic polymers as homopoly-
mers and copolymers widely applied already in the production of
biomaterials. In our opinion new opportunities in this respect are
creating described examples of using ATRP methods for modica-
tion of linear PU among others to an increase in hydrophobicity of
the PU coatings, what is creating great hopes for the synthesis of
newkinds of biomaterials.
ATRP has already been employed in industry, and it can be
expected that in the near future it will surface as one of the pro-
cesses of choice for large-scale production of specialty polymers
such as thermoplastic elastomers, coatings, surfactants, and mate-
rials with medical and pharmaceutical applications, among others.
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-methylene diphenyl diisocyanate

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