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Advances in Polymer Science 270
Philipp Vana Editor
Controlled
Radical
Polymerization
at and from
Solid Surfaces
270
Advances in Polymer Science
Editorial Board
A. Abe, Yokohama, Kanagawa, Japan

A.-C. Albertsson, Stockholm, Sweden
G.W. Coates, Ithaca, NY, USA
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K.-S. Lee, Daejeon, South Korea
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Philipp Vana
Editor
Controlled Radical
Polymerization at and
from Solid Surfaces
With contributions by
E. Bourgeat-Lami F. D’Agosto D. Gigmes A. Goto
J. Jestin H. Jo A. Khabibullin M. Lansalot E. Mastan
K. Matyjaszewski S. Perrier T.N.T. Phan C. Rossner
P. Theato Y. Tsujii P. Vana Y. Zhao S. Zhu
Editor
Philipp Vana
Makromolekulare Chemie
Institut für Physikalische Chemie
Georg-August-Universität G€ottingen
Germany
ISSN 0065-3195 ISSN 1436-5030 (electronic)

Advances in Polymer Science
ISBN 978-3-319-22137-3 ISBN 978-3-319-22138-0 (eBook)
DOI 10.1007/978-3-319-22138-0
Library of Congress Control Number: 2015945965
Springer Cham Heidelberg New York Dordrecht London

© Springer International Publishing Switzerland 2016
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The use of general descriptive names, registered names, trademarks, service marks, etc. in this
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Preface
The tailoring of well-defined polymer structures upon the surfaces of solid mate-
rials constitutes the molecular basis for advanced functional surfaces. The recent
advent of a multitude of controlled radical polymerization methods (also called
reversible deactivation radical polymerization according to IUPAC), which greatly
outperform conventional radical polymerization processes with respect to topolog-
ical control, has had a major impact on this field. These methods allow for the
confinement of polymerizations at surfaces, which may lead to polymer brushes and
other surface-bound polymer arrangements. They also provide macromolecular
architectures of stunning complexity with relative ease, which were far beyond
the wildest dreams of polymer chemists just short time ago. These polymers may
have tailored functionalities that can be used for controlling the interface regime
between the solid material and the soft polymer coverage. The functionality may
also be used to arrange polymer chains and particles in a predetermined manner so
that complicated nano-composites emerge. The polymer and its functionality may
finally be used to modulate surface functions. All these benefits are currently fully
exploited for new surface structures for applications in energy conversion, e.g.,
solar cells; nanomedicine, e.g., drug delivery and tagging; and materials science,
where they are used for the design of functional, responsive, or high mechanical
performance nano-composite materials.
This book presents state-of-the art knowledge about all aspects that are impor-
tant when considering controlled radical polymerization and surfaces. It is intended
to guide the interested polymer chemist through the constantly increasing number
of scientific studies and should help to apply this knowledge for tailoring novel
surfaces. The book starts with four chapters which are dedicated to the four major
controlled radical polymerization methods, namely NMP, ATRP, RAFT and
RTCP. In the second part of the book, a chapter deals with the specific situations
in heterogeneous aqueous media, followed by a contribution about post-
modifications of the polymers formed upon surfaces. The book ends with a chapter
about how tailored polymer from controlled radical polymerization can be used to
fabricate nano-composites. All chapters of this book are by leading scientists in the
v
vi Preface
respective fields and I express my sincerest gratitude to them that they have
contributed in this excellent way to this fine book. I am confident that this issue
of APS will help to make further progress in this fascinating field and will help to
stimulate the development of new applications both in the field of polymer chem-
istry and materials science. I am looking forward to these new exciting steps
forward.
G€
ottingen, Germany Philipp Vana
Contents
Nitroxide-Mediated Polymerization from Surfaces . . . . . . . . . . . . . . . 1

Trang N.T. Phan, Jacques Jestin, and Didier Gigmes
Surface-Initiated Atom Transfer Radical Polymerization . . . . . . . . . . 29
Amir Khabibullin, Erlita Mastan, Krzysztof Matyjaszewski, and Shiping Zhu
Reversible Addition-Fragmentation Chain Transfer Polymerization
from Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
Youliang Zhao and Sébastien Perrier
Surface-Initiated Living Radical Polymerizations Using Iodine,
Organotellurium, and Organic Catalysts . . . . . . . . . . . . . . . . . . . . . . . 107
Atsushi Goto and Yoshinobu Tsujii
Synthesis of Nanocapsules and Polymer/Inorganic Nanoparticles
Through Controlled Radical Polymerization At and Near Interfaces
in Heterogeneous Media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
Elodie Bourgeat-Lami, Franck D’Agosto, and Muriel Lansalot
Post-polymerization Modification of Surface-Bound Polymers . . . . . . 163
Hanju Jo and Patrick Theato
Nanocomposites and Self-Assembled Structures via Controlled Radical
Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
Christian Rossner and Philipp Vana
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
vii
Adv Polym Sci (2016) 270: 1–28
DOI: 10.1007/12_2015_317
© Springer International Publishing Switzerland 2015
Published online: 23 June 2015
Nitroxide-Mediated Polymerization from

Surfaces
Trang N.T. Phan, Jacques Jestin, and Didier Gigmes
Abstract The current chapter gives a general overview on surface-initiated

nitroxide-mediated polymerization (SI-NMP). More particularly, the developed
strategies to perform an SI-NMP process, the various type of substrates including
inorganic and organic supports, and the potential of SI-NMP to prepared advanced
materials are discussed. Based on a selected number of literature examples it
appears that SI-NMP is a versatile and powerful approach to introduce polymer
brushes on surfaces and/or tune polymer surface properties.
Keywords Grafted or brush polymers • Nitroxide-mediated polymerization •

Planar, spherical, and porous surfaces
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 Variation of Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1 NMP from Silicon Oxide Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2 NMP from Metal Oxide Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.3 NMP from Clay Mineral Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2.4 NMP from Metal and Semiconductor Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.5 NMP from Carbon Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.6 NMP from Polymer Surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
T.N.T. Phan and D. Gigmes (*)

Aix-Marseille Université, CNRS, Institut de Chimie Radicalaire, UMR7273, 13397 Marseille
cedex 20, France
e-mail: didier.gigmes@univ-amu.fr
J. Jestin
Laboratoire Léon Brillouin, CEA Saclay, 91191 Gif-sur-Yvette Cedex, France
2 T.N.T. Phan et al.
Abbreviations
3-MPS 3-Methacryloxyproyltrimethoxysilane
AFM Atomic force microscopy
AIBN Azobisisobutyronitrile
APTES 3-Aminopropryl triethoxysilane
ATRP Atom transfer radical polymerization
BlocBuilder MA 2-Methyl-2-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-
dimethylpropyl)aminoxy]propionic acid
BPO Benzoyl peroxide
CNT Carbon nanotube
DLS Dynamic light scattering
DMAc Dimethylacetamide
DMF N,N-Dimethylformamide
DPPC L-Adipalmytoyl-phosphatidylcholine
HEMA 2-Hydroxyethyl methacrylate
LB Langmuir–Blodgett
MAMA-NHS 2-Methyl-2-[N-tert-butyl-N-(1-diethoxyphosphoryl-2,2-
dimethylpropyl)aminoxy]-N-propionyloxysuccinimide
MMA Methyl methacrylate
MMT Montmorillonite
MWNT Multiwalled carbon nanotube
NEXAFS Near-edge X-ray absorption fine structure
NMP Nitroxide-mediated polymerization
OMS Ordered mesoporous silica
P3VP Poly(3-vinylpyridine)
P4VP Poly(4-vinylpyridine)
PAA Poly(acrylic acid)
PBA Poly(n-butyl acrylate)
PtBA Poly(tert-butyl acrylate)
PDMAEA Poly(2-dimethylamino ethyl acrylate)
PHPMA Poly(2-hydroxypropyl methacrylamide)
PNIPAM Poly(N-isopropylacrylamide)
PPTEA Poly[2-phenyl-2-(2,2,6,6-tetramethylpiperidin-1-yloxy)ethyl
acrylate]
PS Polystyrene
PS-b-PCL Polystyrene-block-polycaprolactone
PSMA Poly[styrene-co-(maleic anhydride)]
RAFT Reversible–addition fragmentation chain transfer
SANS Small-angle neutron scattering
SAXS Small-angle X-ray scattering
SG1 N-tert-Butyl-N-[1-diethylphosphono-(2-2-dimethylpropyl)
nitroxide]
SI-NMP Surface-initiated nitroxide-mediated polymerization
SWNT Single-walled carbon nanotube
Nitroxide-Mediated Polymerization from Surfaces 3
TEM Transmission electron microscopy

TEMPO 2,2,6,6-Tetramethylpiperidinyl-1-oxy
TEMPO-Br 1-Oxo-2,2,6,6-tetramethylpiperidinium bromide
TIPNO 2,2,5-Trimethyl-4-phenyl-3-azahexane-3-oxyl
TSPMA 3-(Trimethoxysilyl)propyl methacrylate
VBC 4-Vinylbenzyl chloride
XPS X-ray photoelectron spectroscopy
1 Introduction
Surface modification with thin polymer films is considered one of the most attrac-
tive ways of obtaining “smart” surfaces in response to external stimuli such as
solvent, temperature, pH, and ions. This modification imparts new surface proper-
ties such as wettability, biocompatibility, corrosion resistance, and friction. Thin
polymer films can either be prepared by spin-coating with a polymeric solution or
by covalent attachment of one end of a polymer chain to the surface. The latter
technique gives rise to polymer brushes [1]. The “grafting-from” approach is one of
two strategies commonly used to attach polymers to a substrate surface. This
approach has been largely developed thanks to controlled or “living” polymeriza-
tion techniques (CLRP), because they allow accurate control over polymer thick-
ness, density, composition, and architecture [2]. Polymerizations can be performed
on substrates exhibiting different topologies, such as planar wafers, spherical
particles, or a confined environment, and are compatible with a broad range of
monomers. Different controlled radical polymerization (CRP) techniques such as
atom transfer radical polymerization (ATRP), reversible–addition fragmentation
chain transfer (RAFT), and nitroxide-mediated polymerization (NMP) have been
used for the preparation of functionalized surfaces [2–4]. However compared with
other CRP techniques, NMP is underexploited and has so far been the subject of
only a few review articles. Indeed, initially, NMP was limited to a small range of
polymerizable monomers (i.e., only styrene and its derivatives). Meanwhile, the
development of more potent nitroxides has greatly expanded the number of mono-
mers (acrylates and acrylamides) compatible with the NMP process [5]. An impor-
tant advantage of surface-initiated NMP (SI-NMP) is that no further addition of
metals or metal complexes is necessary. Hence, no extra purification steps are
required and the likelihood of introducing impurities is also strongly limited. This
specific feature is particularly attractive for applications where the purity of
polymer-based materials is of high importance, such as in biomedical and elec-
tronic fields.
NMP is controlled by the persistent radical effect (PRE) [6] that can be described
as follows: If we consider a diamagnetic compound (RY) that decomposes
homolytically to generate two radical species at both the same time and the same
rate, the PRE occurs when one of the radical species (Y∙) is more persistent than the
other (R∙). Typically, at the early stages of the reaction, the concentrations of the
Scheme 1 Homolytic decomposition of a diamagnetic compound RY, with R∙ being transient and
Y∙ persistent
Initiation R1 R1
D
Bicomponent R R + N O N O + R
R2 R2
R1 R1
D
or Monocomponent N OR N O + R
R2 R2
Propagation
Y1 Y1
R1 R1
D
R CH 2 C O N R CH 2 C + O N
R2 R2
Y2 Y2
+M
Scheme 2 Mechanism of nitroxide-mediated polymerization
two radical species are strictly equivalent. However, after a short period of time
some self-termination reactions of the transient radical (R∙) are unavoidable, lead-
ing to a decrease in its concentration relative to that of the more persistent radical
species. Therefore, recombination of the transient and persistent radicals becomes
progressively favored, rather than self-reaction of the transient radical (Scheme 1).
This specific feature of the PRE explains many highly selective radical cross-
coupling processes, including the NMP process.
Hence, NMP is grounded on a reversible termination equilibrium between
the propagating (macro)radical and the nitroxide (Scheme 2) [5]. Typically, the
nitroxide plays the role of controlling agent and, thanks to the PRE, the growing
polymer chains mainly have a (macro)alkoxyamine-based chemical structure.
These (macro)alkoxyamines (the so-called dormant species) are able to cleave
homolytically to yield the propagating radical and the nitroxide once again. Inter-
estingly, this equilibrium is only ruled by a thermal process.
Initially, NMP was conducted using a bicomponent initiating system (i.e., a
conventional radical initiator in the presence of a nitroxide). Obviously, this system
is attractive from an economic and practical point of view. However, with a
bicomponent initiating system, the polymerization kinetics and the molecular
weight of the polymer chains are difficult to control. Indeed, with conventional
radical initiators it is difficult to exactly determine the number of generated
radicals. Moreover, compared with the radical initiator concentration, a large
excess of nitroxide decreases the polymerization rate by shifting the equilibrium
N N N P(O)(OEt) 2
O O O
TEMPO TIPNO SG1
Fig. 1 Structure of nitroxides frequently used for SI-NMP. TEMPO 2,2,6,6-tetramethylpi-

peridinyl-1-oxy; TIPNO 2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxyl; and SG1 N-tert-butyl-N-
[1-diethylphosphono-(2,2-dimethylpropyl)] nitroxide
of the propagating step towards the dormant species. To overcome these drawbacks,
the use of a monocomponent initiating system is preferred. This approach consists
in using an alkoxyamine that decomposes homolytically, under heating, to afford
the corresponding alkyl radical as initiator and nitroxide as controller. The disso-
ciation rate constant of the alkoxyamine is of major importance in ensuring efficient
establishment of the PRE and, therefore, an efficient CRP process [5].
Typically, surface-initiated NMP is achieved by following one of two main
strategies. As an example of the first strategy, a conventional radical initiator is
anchored to the surface and then the polymerization reaction is performed in the
presence of free nitroxide, which allows the in situ formation of (macro)
alkoxyamine. In the second strategy, a preformed alkoxyamine is first attached to
surface; in this case, the initiation and polymerization control proceeds from a
monocomponent system. Depending on the chemical nature of the surface sub-
strate, various strategies can be envisioned for grafting the initiator to the surface.
For instance, initiator anchoring can be achieved using covalent bonding, electro-
static interaction, or even hydrogen bonding. The nitroxides frequently used for
SI-NMP are TEMPO, TIPNO, and SG1 (see Fig. 1 for structures).
This review focuses on NMP initiated from the surface of different substrates
such as silicon, metal oxide, carbon, and polymer. The possible architecture and
composition of polymer chains grown from the surface is also discussed. Applica-
tion of surfaces modified with polymer films prepared by NMP is briefly described.
2 Variation of Substrates
SI-NMP has proven efficient for the growing of polymer chains from various
substrates. To reach this goal, the surface is usually modified with a suitable
initiator or mediator, introduced in either a single step or via a multistep procedure.
In this section, the preparation of grafted polymer via SI-NMP from different
substrates such as silicon oxide, metal oxide, metal and semiconductor, mineral
clay, carbon-based materials, and polymer surfaces is discussed. For each class of
substrate, the discussion focuses on the surface chemistry available for introducing
functional groups that allow SI-NMP.
2.1 NMP from Silicon Oxide Surfaces
Silicon oxide is probably one of the most studied substrates used to graft polymer
chains via NMP. Typically, silicon wafers, glass, quartz slides, porous and
non-porous particles, as well as membranes are used in the SI-NMP process.
To introduce a functional group that can initiate or mediate SI-NMP from silicon
oxide surfaces, organosilane is often used. Prior to the grafting step, silicon oxide
materials are first treated with a H2SO4/H2O2 mixture or oxygen plasma to clean the
surface and optimize the number of silanol groups involved in further reaction. In
this case, a thin layer of water is formed on the silicon oxide surface. The
introduction of organosilane onto this surface is obtained after surface adsorption,
hydration, and salinization steps. In this procedure, the silanol functions (Si–OH)
present at the silicon oxide surface are able to undergo a condensation reaction with
different types of organosilane reagents, such as R-SiMe2Cl, R-SiCl3, or R-Si
(OMe)3, and R-Si(OEt)3, leading to siloxane bonds Si–O–Si [7].
2.1.1 NMP from Silicon Oxide Planar Surfaces
The first example of polymer synthesis from SI-NMP was reported by Hawker’s
group [8]. The authors immobilized a TEMPO-based alkoxyamine on the surface of
an oxidized silicon wafer via the reaction of chlorosilane groups present on the
alkoxyamine with the silanol groups of the oxidized silicon wafer in the presence of
triethylamine as catalyst. Then, polystyrene (PS) brushes were obtained from NMP
of styrene. For planar substrates with low specific surface areas, such as silicon
wafer in this example, the concentration of persistent radicals in the reaction
medium is low because of the limited number of initiator molecules on the wafer
surface. To overcome this drawback, a predetermined amount of free alkoxyamine
(called sacrificial initiator) can be added to the reaction mixture to control the
polymerization process (Scheme 3). Addition of this sacrificial alkoxyamine pro-
vides a sufficiently high concentration of free nitroxide in the polymerization
mixture, which controls the polymer chain growth of both immobilized and soluble
initiators. However, the addition of free alkoxyamine leads to the formation of non-
surface-attached polymers, which have to be removed from the resulting polymer
brushes. The authors found that the number-average molecular weight (Mn) and the
dispersity of the grafted PS were similar to those of the free polymer chains in
solution. Following this strategy, homopolymer and random copolymers grafted on
surfaces were prepared with control of molar mass or thickness of the brushes (up to
80 nm), while maintaining low dispersities. The living nature of the polymerization
was demonstrated by re-initiation of the end-capped chains to form the
corresponding block copolymer brushes.
Following this strategy, Hawker and coworkers [9] successfully initiated the
polymerization of tert-butyl acrylate from the surface of oxidized silicon wafer
functionalized with 1 in the presence of the TIPNO-based alkoxyamine 2 and
TIPNO (Scheme 4) [10]. The rapid exchange of free nitroxide between bound
N
N
O
N
n
O
O
O N
O
Toluene/Et3N
8
O
O
8
RT, 18h
8
125°C, 24h
Si
R R Si
Cl Si
R R
+ O R R
O
Si/SiO2 Si/SiO2
Si/SiO2
Scheme 3 Styrene SI-NMP from silicon wafer grafted with a TEMPO-based alkxoyamine
R N
O O N
Cl Si 8 O
1 2
Scheme 4 Structure of alkoxyamines used for SI-NMP of tert-butyl acrylate on oxidized silicon
wafer. Reported by Hawker and coworkers [9]
macroalkoxyamines on the surface and nitroxide in solution allowed the controlled

formation of poly(tert-butyl acrylate) (PtBA) chains from surfaces. The thickness
of polymer brushes (100–200 nm) could be controlled by varying the molar ratio of
tert-butyl acrylate and alkoxyamine 2. The PtBA brushes were then patterned using
photolithographic techniques to yield original patterned poly(acrylic acid) chains,
leading to discrete hydrophobic and hydrophilic domains.
TEMPO-functionalized silicon wafers or glass slides were also used to prepare
SI-NMP-made polymer brushes on surfaces [11–19]. Chapel and colleagues
employed a similar system, using an ester instead of ether linkage and
triethoxysilane as reactive anchor group on a C11 spacer [11, 17]. With this reactive
system, molecules spread on water gradually become amphiphilic when
triethoxysilane end groups are converted to trihydroxy groups. Taking advantage
of this amphiphilic character, stable monolayers of various densities can be depos-
ited by the Langmuir–Blodgett (LB) technique onto silicon wafers. Hydrolysis
and/or condensation of the triethoxysilane end groups allows formation of a Si–
O–Si covalent bond with the oxidized silicon wafer. Surface-initiated styrene
polymerization was performed on a system with different initiator densities. In
addition, immobilization of alkoxyamine initiators and subsequent surface-initiated
styrene polymerization was performed on an atomic force microscopy (AFM) tip by
LB transfer [12].
R
R
O N X
R O N
O N OMe
R
EtO 4 (R=Me, X=H) 6 7

EtO Si 9 O 5 (R=Et, X=OMe)
EtO
Scheme 5 Alkoxyamines and nitroxide used for SI-NMP of tert-butyl acrylate on oxidized silicon
wafer. Reported by Studer and coworkers [16]
Scheme 6 (a) AFM image of surface after SI-NMP of styrene with 5. (b) AFM image of surface
after SI-NMPP of n-butyl acrylate with 5 (insets show cross-sections; scale bars: 2.5 μm).
Reproduced from Brinks et al. [16] with permission from Wiley
LB lithography for spatially controlled attachment of initiator to form regular

stripes of PS and poly(n-butyl-acrylate) (PBA) brushes was reported by Studer and
coworkers [16]. Mixed monolayers of L-adipalmytoyl-phosphatidylcholine (DPPC)
and TEMPO-derived alkoxyamines 4 or 5 (Scheme 5) were transferred by the LB
technique onto oxidized silicon wafer in regular stripes with submicrometer lateral
dimensions. Physisorbed DPPC was removed by washing, and NMP of styrene
from the surface of silicon wafer covalently bonded to 4 was performed at 125 C
for 24 h in the presence of 6 as sacrificial polymerization regulator. NMP of n-butyl
acrylate was conducted with a surface modified with 5 in the presence of 7 at 105 C
for 24 h. Polymer stripe width was controlled by the concentration of alkoxyamine
in the mixed phase and adjusted from about 0.2 to 1.3 μm. The height of the stripes
increased to 8 0.2 nm for PS and 4.7 0.2 nm for PBA (Scheme 6).
LB reactive deposition was also employed for anchoring of triethoxysilyl
alkoxyamine derivatives of TEMPO 8, SG1 9, and TIPNO 10 nitroxides to silicon
substrates (Scheme 7) [17]. The nitroxide polarity and, therefore, the behavior of
the corresponding alkoxyamine at the air–water interface of the LB trough had a
O O
O
OEt
EtO O N P
EtO O N
EtO Si 10
O OEt
EtO Si O
10 EtO
EtO
8 9
O N
10
EtO
EtO Si 10O
EtO
Scheme 7 Triethoxysilyl alkoxyamines derivatives of TEMPO 8, SG1 9, and TIPNO 10

nitroxides
strong influence on the grafting density and the stretching of the resulting PS
brushes. The TEMPO- and TIPNO-based alkoxyamines yielded relatively dense
PS brushes, whereas the SG1-based alkoxyamine yielded brushes with low grafting
densities and stretching as a consequence of the polar phosphorylated group.
Surface-tethered styrene-based homopolymer and diblock copolymers brushes
bearing fluorinated alkyl side groups or ethylene glycol oligomers were produced
with controlled chemical architecture and high coverage using SI-NMP on planar
oxidized silicon surfaces [14, 15]. The silicon oxide surfaces were first modified
with a chlorosilyl-functionalized TEMPO derivative (Scheme 8). In the case of
diblock copolymer brushes, the second block was always detected at the polymer–
air interface, as shown by angle-resolved X-ray photoelectron spectroscopy (XPS)
and water contact angle measurements. Near-edge X-ray absorption fine structure
(NEXAFS) analysis revealed an orientation of fluorinated side chains that could be
correlated with surface stability upon exposure to water. Surface grafted with oligo
(ethylene glycol)-containing polymer brushes possessed a superior ability to inhibit
protein and cell adhesion compared with surface assemblies with deposited oligo
(ethylene glycol).
Tethered alkoxyamines were also obtained in situ following a two-step proce-
dure. First, 3-(trimethoxysilyl)propyl methacrylate (TSPMA) was attached to the
surface. Then, the methacrylate function was allowed to react, under heating, with
AIBN in the presence of TEMPO to afford the corresponding alkoxyamines. From
this alkoxyamine-coated silicon, PS and poly(2-hydroxyethyl methacrylate)
(HEMA) were then successfully prepared [20]. The novelty of this report is that
micropatterning of the silicon surface was controlled by a combination of SI-NMP
and SI-ATRP. The ATRP initiator was covalently immobilized via UV-induced
hydrosilylation of 4-vinylbenzyl chloride (VBC) with the (hydrofluoric acid-
etched) hydrogen-terminated silicon (Si–H) microdomains to produce a
micropatterned and Si–C bonded VBC monolayer.
O N N O
N O
q
6
p
1) Styrene-R1 R2
2) Styrene - R2
R1
O
5
(CF2)nF
12a) R1 = R2 = O
O
5
O
12b) R1 = R2 = O m
Si
n = 6, 8
O 12c) R1 = H
(CF2)nF m = 3, 7 Si
11 R2 = O
O
Si/SiO2
12d) R1 = H
12 a-d
O
R2 = O m
Si/SiO2
Scheme 8 Synthesis of surface-grown styrene-based homopolymer and diblock copolymer

brushes bearing fluorinated alkyl side group and ethylene glycol oligomer
Recently, Studer and coworkers [19] prepared polymer brushes bearing

α-hydroxyalkylphenylketone moieties as photoreactive polymer backbone using
SI-NMP with 11. Photoreactive polymer brushes (with thickness up to 60 nm) can
undergo Norrish type I photoreaction upon irradiation to give surface-bound acyl
radicals, which are trapped with functionalized nitroxides to give the corresponding
acylalkoxyamines. This post-polymerization modification provided functionalized
polymer brushes bearing cyano, poly(ethylene glycol), perfluoroalkyl, and biotin
moieties.
Vapor phase polymerization from SI-NMP of various vinylic monomers resulted
in polymer brushes with greater thicknesses than those formed by the solution phase
process [21]. To explain this result, the authors supposed a more efficient reaction
on the surface as a result of prolongation of the mean path of vaporized monomers
in a vacuum, higher thermal energy of the monomer, and the possibility of adjusting
the reaction parameters independently. Thin films of PS grafted polymer, poly
(acrylic acid) (PAA), poly(2-hydroxypropyl methacrylamide) (PHPMA), and
poly(N-isopropylacrylamide) (PNIPAM) were prepared with thicknesses of a few
nanometers to submicrometers. This process was also used for the preparation of
block copolymers (e.g., PS-b-PAA and PAA-b-PS-PHPMA). It is important to
mention that solution phase polymerization of AA, HPMA, and NIPAM is impos-
sible with TEMPO-based alkoxyamines.
SI-NMP can also be carried out using an initiator/nitroxide bimolecular system
[22]. In this strategy, an azo-based initiator functionalized with chlorosilyl groups
was first attached to the silicon wafer after immersion of the substrates in a toluene
solution containing the azo derivatives. The formation of PBA brushes with thick-
ness of 4–14 nm using two different azo initiators (AMCl and ATCl) was performed
R R H3C CN H3C CN R R
O O
Cl N N Cl
O O
Scheme 9 Chemical structure of the chlorosilyl derivatives of azo initiators ATCl (R¼Cl) and
AMCl (R¼CH3)
in the presence of SG1 as controlling agent (Scheme 9). Elaboration of block

copolymers by re-initiation of PBA growth from macromolecular chains grafted
on a flat substrate with different monomers was also achieved.
Recently, SI-NMP using a bimolecular system was applied to the preparation of
PS brushes. In this study, the initiator sites were generated from the silicon wafer
surfaces by treating the latter with hydrogen plasma at atmospheric pressure
[18]. According to the authors, the dissociation of molecular hydrogen in gas
phase collisions produces hydrogen plasma, which can react with surface sites
and surface-adsorbed water to form surface-activated sites. Precise control of
plasma treatment time and radio frequency power allows a dense surface coverage
of radical initiators to be obtained, from which vinyl monomers can combine to
form surface-grafted polymer chains. Growth of PS film was thus achieved in the
presence of TEMPO and exhibited a linear increase with respect to time, resulting
in a polymer layer thickness of 28 nm.
2.1.2 NMP from Silicon Oxide Particle Surfaces
Synthesis
SI-NMP from silicon oxide surfaces has not been confined to planar surfaces, but
has also been extended to colloidal supports as well as particle surfaces. As with
silicon oxide planar surfaces, the most convenient strategy for introducing initiator
onto the SiO2 particle surfaces is to first graft functional alkoxyamines on their
surfaces and then perform the polymerization reaction. A number of TEMPO,
TEMPO-derivative, TIPNO, or SG1-based alkoxyamines bearing trichlorosilane
(–SiCl3), trimethoxysilane [–Si(OMe)3], and triethoxysilane [–Si(OEt)3] as the
functional group have been prepared. A complete review of SI-NMP from SiO2
particle surfaces has been recently published [5]. Chain conformation is a crucial
factor in determining the macroscopic properties (solution, gel, composite, thin
film, etc.) of the final grafted nanoparticle system. NMP enables the preparation of
well-defined grafted silica nanoparticles. Therefore, control of polymerization
opens the way to probe the conformation of the grafted chains at the surface of
the nanoparticles and to analyze whether this conformation is affected by grafting
as a function of various parameters such as the molecular mass of the grafted
chains, grafting density, solvent quality, nature and shape of the surface (surface
curvature), and interactions of nanoparticles in solution.
Conformation of Grafted Polymer Chains
Numerous works have been carried out on spherical grafted brushes to predict the
conformation of grafted chains using theory [23, 24] and/or numerical simulations
[25, 26]. Experimental validation is limited to a small number of techniques for
evaluating the typical size of the grafted chain: rheology for the viscosimetric
radius Rη, dynamic light scattering (DLS) for the hydrodynamic radius Rh [27,
28], and small angle X-ray or neutron scattering (SAXS or SANS) for the radius of
gyration Rg. Viscosimetric or DLS measurements give a total value (including the
nanoparticle size) that can be affected by nanoparticle concentration or nanoparticle
aggregation and/or percolation. The accuracy of such determinations can be
improved using SANS combined with neutron contrast variation, enabling direct
determination of the radius of gyration of the grafted chains by matching the
scattering of the core particles while controlling the colloidal stability of the
solution by determination of interparticle structure factors. In solution, contrast
variation is simply performed by adjusting the ratio of hydrogenated and deuterated
solvent to obtain the desired values of neutron scattering length density for both the
particle and the grafted polymer. This was first described by Chevigny et al. [29] for
silica nanoparticles grafted with PS chains. The efficiency of the polymerization
was improved by adding free initiator at the beginning of the reaction. At the final
stage, free polymer chains were removed by ultrafiltration. The grafted brushes
were finely characterized by fitting the SANS curves with different models (core–
shell and Gaussian chain mode) to extract the physical parameters of the grafted
brushes: number of chains per particle, molecular mass, and radius of gyration of
the grafted chains. An example of such a curve is given in Scheme 10a.
A significant feature of the curve is the decrease in intensity as a function of
scattering vector (Q2) for the high Q region, indicating that the grafted chains are
still Gaussian. The extension of the grafted layer h ¼ 2Rg grafted was ~1.30 times
larger than the corresponding Gaussian chain in theta solvent (2Rg bulk, with Rg
bulk ¼ 0.275 Mw ), as determined by size-exclusion chromatography (SEC) after
0.5
the cleaving process. This indicates stretching of the chain at the surface of the
particle. Such a stretching, which can be explained by excluded volume interactions
with lateral neighboring chains, has been described by Alexander in terms of
scaling laws of the grafting density [24]. For a layer grafted on a planar surface,
the extension of the grafted layer is expected to be h ¼ a0N1/3 for a good solvent and
h ¼ a0N1/2 for a theta solvent, where a0 is the monomer length and N the number of
monomers. In addition, the effect of surface curvature r02/5 has to be taken into
account; it reduces the extension of the grafted layer to h ¼ N1/2σ 1/2r02/5 for the case
of theta solvent [26]. Replacing free initiator by controller (SG1) in the reaction
enables variation of the molecular mass of the grafted chain in the range 5–50 kg.
mol-1 [32]. Whatever the N value, a systematic agreement is found between the
extension of the grafted brush deduced from the fitting analysis h ¼ 2Rg grafted and
the theoretical prediction derived from the scaling law h ¼ N1/2σ 1/2r02/5. Genevaz
and colleagues (unpublished results) have recently adapted the previous NMP
protocol to the grafting of a diblock copolymer PtBA-b-PS at the surface of silica
2 3
10 10
(a) (b)
2
10
1
10
I (cm )
I (cm )
1
10
-1
-1
0
10
0
10
-1
10
-1
10
-2 -2
10 10
-3 -2 -1 -3 -2 -1 0
10 10 10 10 10 10
Q (Å-1) Q (Å-1) 10
10
(c)
Dispersed
e/Rg 1
Aggregated
0,1
0,1 1
R
Scheme 10 (a) SANS curve of silica nanoparticles with PS-grafted brush in solution (black dots)
and the corresponding fitting calculation (red line). From Chevigny et al. [29]. (b) SANS curve of
silica nanoparticles with PS-grafted brush in melt (black dots) and the corresponding fitting
calculation (red line). From Chevigny et al. [30]. (c) Variation of the grafted brush conformation
as a function of the nanoparticle dispersion in the host polymer matrix. From Chevigny et al. [31]
particles by associating dynamic light scattering (DLS) and SANS. The motivation
of this work was to make spherical brushes with an interface of tunable dynamics
using a combination of a block (PtBA) with low glass transition temperature (Tg)
and a block (PS) with high Tg. They showed that the diblock conformation behaved
in the same way as the homopolymer chain and that the grafting had no influence on
the chain extension when the chain is close to the Kuhn length. Robbes et al. [33]
grafted PS chains on magnetic nanoparticles (maghemites, γ-Fe2O3) using NMP. In
contrast to the silica “single sphere” particles, in solution maghemites form linear
clusters of three to four primary particles from which the PS chains grow under
controlled polymerization. It is possible to directly probe the influence of surface
curvature on the extension of the grafted chains for a given grafting density and
under theta solvent conditions; indeed, the extension of the grafted chain
(h ¼ 18 nm) was found to be intermediate between the pure spherical case
(h ¼ 11 nm) and the pure plan geometry (h ¼ 44 nm). Regarding the question of
the conformation of grafted chains in solution, it is interesting to look at the
corresponding conformation in nanocomposites when spherical brushes are mixed
with identical free chains. This was probed by Chevigny et al. [30] using a statistical
hydrogenated–deuterated PS matrix that matched the particle scattering in SANS
experiments; the silica becomes invisible to neutrons in the matrix, and only the
deuterated corona contributes to the signal. The resulting curve (presented in
Scheme 10b) was perfectly fitted by a Gaussian model and showed partial collapse
of the grafted brushes from solution (12 nm) to film (6 nm), corresponding to a wet–
dry transition driven by entropy mixing between the grafted and free chains. By
varying the dispersion state of the nanoparticles inside the matrix, the same authors
[31] demonstrated a second transition from partial to complete collapse of the
spherical brushes, associated with the formation of compact aggregates inside the
film (Scheme 10c).
2.1.3 NMP from Porous Silicon Oxide
In comparison with colloidal particles such as silica or planar surfaces such as

silicon wafer, SI-NMP from ordered mesoporous silica (OMS) has been much less
investigated. Alongside the usual issues of SI-CRP from dense substrates, such as
initiator and deactivator concentration or initiator efficiency, the porous nature of
OMS (high specific surface area, high porous volume, pore morphology, pore
diameter, and pore connectivity) brings to the system new complexity, such as
diffusion of reactants in a confined space. The first SI-NMP from OMS was
performed by Lenarda et al. at the inner surface of MCM-41 mesoporous silica
[34]. Typically, the MCM-41 silica was modified following a three-step grafting
procedure: first, reaction with 3-aminopropyltriethoxysilane, then terephthaloyl
chloride, and finally 1-hydroxy-2-phenyl-2-TEMPO-ethane. The styrene polymer-
ization was shown to occur inside the mesoporous silica channels. It should be
mentioned that partial filling of the pores decreased the surface area of the MCM-41
silica without destroying its structural and morphological characteristics. More
recently, the SI-NMP of styrene was performed from various types of ordered
mesoporous silica particles with different morphologies and pore sizes, using an
SG1-based alkoxyamine derived from BlocBuilder MA initiator [35]. Whatever the
pore morphology and pore size, the polymerization kinetics were similar in all
cases, but with important differences in the molar mass distribution. The authors
showed that for good diffusion of the reactants, large pore sizes of 5 nm were
adequate and that the porous morphology of the particles is of high importance,
particularly pore connectivity.
O O
O P O N OMe O P O N OMe
O O
Styrene n
O O
TiO2
TiO2
or Fe3O4
or Fe3O4
nanoparticles
nanoparticles
Scheme 11 Polymerization of styrene on metal oxide nanoparticles
2.2 NMP from Metal Oxide Surfaces
SI-NMP from metal oxide surfaces is mainly performed from previously modified
titanium or iron oxide substrates. Titanium oxide (TiO2, d ¼ 15 nm) and magnetite
(Fe3O4, d ¼ 10 nm) nanoparticles chemically modified with 4-methoxy-TEMPO-
based alkoxyamine by a phosphonic acid group were utilized by Takahara and
coworkers for the preparation of PS (Scheme 11) and poly(3-vinylpyridine) (P3VP)
brushes [36–40]. The grafting densities of PS chains on TiO2 particles were
estimated to be 0.04–0.28 chains nm2 whereas those on Fe3O4 particles were
0.12–0.2 chains nm2. Functionalized nanoparticles showed stable dispersibility in
good solvents of PS without losing their physical properties. In the case of P3VP-
modified magnetite, the particles gave a stable dispersion in good solvents thanks to
pyridinium formation through either protonation of the pyridine rings with an acidic
solution or quaternization with an aqueous solution of iodomethane [40].
In a similar procedure, Binder et al. used a TIPNO-based alkoxyamine bearing a
1,2-diol function for its attachment onto iron oxide. This system was used for the
preparation of core–shell Fe2O3 nanoparticles with a well-defined PNIPAM shell
(Scheme 12) [41]. The polymerization reaction was performed in N,N-dimethyl-
formamide (DMF) at 150 C. Under these conditions, monomer conversion reached
90% and experimental Mn was 5,600 g mol1. Poly (4-vinylpyridine) (P4VP)
brushes were prepared by SI-NMP on the surface of
3-methacryloxyproyltrimethoxysilane (3-MPS)-modified magnetite nanoparticles
with an average diameter of 30 nm. The NMP-made P4VP polymer brushes were
obtained at 130 C using 4-hydroxyl-TEMPO free radical as controlling agent and
benzoyl peroxide (BPO) as initiator [42].
Recently, an efficient three-step grafting-from procedure was developed to
obtain well-controlled PS grafted magnetic γ-Fe2O3 nanoparticles [33]. In the
first step, after modification of the surface charge of the nanoparticles and then
replacement of H2O by dimethylacetamide (DMAc), 3-aminopropryl
trethoxysilane (APTES) was allowed to react with the surface. The corresponding
amino-modified nanoparticles were then reacted with MAMA-NHS alkoxyamine
(Scheme 13) to afford nanoparticles functionalized with SG1-based alkoxyamine.
In the last step, polymerization of styrene was performed from the previously
modified nanoparticles. The grafting-from strategy was also used to graft poly
[styrene-co-(maleic anhydride)] (PSMA) chains from the Fe3O4 nanoparticle
O N O N
n
O O NH
N
H
DMF / 150°C
O O
O O
7 7
OH OH
g -Fe2O3 g-Fe2O3
OH OH
Scheme 12 Grafting-from of N-isopropyl acrylamide from the surface of γ-Fe2O3 nanoparticles

attached to TIPNO-based alkoxyamine bearing a 1,2-diol
SG1 O
O
O Si NH2 N
OEt O
DMAc O
+ EtO Si NH2 O Si NH2 MAMA-NHS O
RT, 12h
-Fe2O3 OEt O
DMAc, 0°C, 1h
O Si NH2
In
O Si
O Si O
O
O
O
SG1 Styrene O Si N SG1
O Si N H
H
120°C, 6h O n
O
O Si
O Si
In
Scheme 13 Grafting-from strategy for preparation of well-defined PS-grafted magnetic γ-Fe2O3

nanoparticles
surface with TEMPO moieties [43]. For this, TEMPO was first immobilized onto
Fe3O4 nanoparticles by the nucleophilic substitution reaction between
1-oxo-2,2,6,6-tetramethylpiperidinium bromide (TEMPO-Br) and hydroxyl groups
on the Fe3O4 surfaces. In the second stage, PSMA-Fe3O4 was synthesized using
TEMPO-immobilized Fe3O4 in the presence of styrene and maleic anhydride. Free
TEMPO was also present in the system to enhance control of polymerization.
There has been only one report describing SI-NMP from a metal oxide other than
those of titanium and iron, namely from a copper oxide surface [44]. In this study,
poly(ionic liquid) was grafted onto micro/nanoscale CuO/Cu surfaces by
bimolecular-initiated polymerization with TEMPO nitroxide. For this purpose,
the peroxide groups were first introduced onto micro/nanoscale CuO surfaces by
reaction of 3-chloropropyltrimethoxysilane (immobilized on the CuO surface) with
Cl
Cl Cl
O O
O O
OOH
Si Methanol
R R Si Si
Cl RT, 24h O Dioxane / Na2CO3
O O
+ O O 12h
Si Si
O
OH OH OH O O
O O
CuO substrate
CuO substrate
CuO substrate
N
TEMPO, xylene, 130°C N
PF6
N
PF6 CuO substrate
Scheme 14 Process of poly(ionic liquid) growth at CuO surface
tert-butyl hydroperoxide. Polymerization of 1-(4-vinylbenzyl)-3-butylimidazo-

liumhexafluorophosphate, an ionic liquid monomer, from the peroxide-activated
CuO surface in the presence of TEMPO led to the formation of polymer brushes
(Scheme 14).
2.3 NMP from Clay Mineral Surfaces
The main approach for immobilization of functional groups that can initiate or
mediate SI-NMP on clay mineral surfaces is based on noncovalent electrostatic
interactions. Indeed, clay minerals present the ability to exchange cations in the
interlayer spacing with other ionic species present in solution. Sogah and coworkers
were the first to report an efficient approach for the direct synthesis of dispersed SI-
NMP-made silicate nanocomposites. Typically, they performed an intergallery
polymerization via a montmorillonite (MMT)-anchored TEMPO-based
alkoxyamine initiator bearing a benzyltrimethylammonium 13 (Scheme 15) moiety
[45]. Other alkoxyamines bearing cationic groups were also attached on MMT
surfaces. A cationic alkoxyamine 14 based on 2,6-diethyl-2,3,6-trimethyl-piperi-
dine-4-hydroxy-N-oxyl nitroxide was directly intercalated into MMT layers. PBA
chains were then grown, exhibiting tunable Mn in the 1,000–14,000 g mol1 range
and a dispersity of 1.5, allowing facile re-dispersion of the resulting composite in
apolar solvents [46]. In another example, a three-step procedure was proposed by
Shen et al. for grafting PS chains on the surface of MMT [47]. The first step
O
O N
O N
HO
O
N Cl
N Cl 15
13
O
OEt
O N P
OEt
O N OH
N N O
H
Cl
14 16
N Cl
Scheme 15 Structure of cationic alkoxyamines used for SI-NMP from clay surfaces
consisted in attaching 2-methacryloyloxy ethyl trimethylammonium chloride to the

surface of MMT by an ion-exchange reaction. Then, the alkoxyamine-
functionalized MMT was reacted with the previously introduced methacrylate
function in the presence of BPO and TEMPO at 90 C. PS chains with controlled
Mn and low dispersity were then successfully grown from the MMT surface by
SI-NMP. Polystyrene-block-polycaprolactone (PS-b-PCL) diblock copolymers
were also grafted to MMT surfaces in one-step in situ living polymerization from
a silicate-anchored bifunctional initiator based on TEMPO 15 (Scheme 15) via
divergent chain growth [48]. Recently, Paulis et al. performed SI-NMP of methyl
methacrylate (MMA)/butyl acrylate using modified MMT macroinitiator [49]. The
macroinitiator was synthesized by NMP of vinylbenzyl trimethylammonium chlo-
ride, MMA, and styrene at 90 C using Blocbuilder MA as alkoxyamine. The
obtained macroinitiator of 1,000 g mol1 was exchanged with the sodium cations
of MMT to yield surface-modified reactive MMT. SI-NMP of MMA/butyl acrylate
from reactive MMT surfaces allowed exfoliation of the clay. The composite was
then used as master batch in the mini-emulsion polymerization of MMA/butyl
acrylate.
A similar strategy has been used to allow SI-NMP from other clay minerals such
as laponite [50] and saponite [51]. In the case of laponite, a SG1-based alkoxyamine
bearing an ammonium group 16 (Scheme 15) was first immobilized by cation
exchange (Scheme 16) [50]. Then, PS chains were obtained from its surface in
the presence of a sacrificial alkoxyamine initiator to afford composites exhibiting
improved colloidal stability in inorganic solvent. Transmission electron
SG1
N
Ion exchange Styrene
Styryl-SG1
SG1
Toluene, 110°C, 32h
N
SG1
N Cl
bound polymer
free polymer
Scheme 16 SI-NMP of styrene from laponite clay platelets
microscopy (TEM) performed on these samples demonstrated a completely exfo-

liated structure of the clay tactoids within the polymer matrix.
Alternatively, different reports describe the immobilization of free-radical initi-
ators carrying cationic groups on mineral clay surfaces for subsequent SI-NMP of
vinylic monomers performed in the presence of an efficient nitroxide mediator [52–
55]. For example, Mittal reported the immobilization of 4,4-azobis(4-cyanovaleric
acid)-based initiator bearing long alkyl chains and two cationic groups for subse-
quent SI-NMP of lauryl methacrylate in the presence of SG1 [52]. The same
approach was employed by Billon and coworkers for the preparation of (co)
polymer/mica composites [53–55]. Mica SI-NMP proceeds in two steps: (1) mica
surface modification via ion exchange of 2,2-azobis(isobutyramidine hydrochlo-
ride) as a free-radical initiator bearing a cationic moiety, and (2) SI-NMP of butyl
acrylate performed from the initiator-bound mica in the presence of free SG1
nitroxide. In the case of copolymer/mica composites, polymerization of butyl
acrylate followed by polymerization of a mixture of styrene and a modified alizarin
dye monomer were performed. Although control was lost during the polymerization
of the second block, colored diblock copolymer/mica composites were indeed
obtained [54]. Interestingly, the colors of poly(styrene-co-alizarin)/mica compos-
ites were strongly related to both the adsorption density of macromolecular chains
on the mica surface and the dye content [55].
Besides noncovalent interactions, covalent immobilization has also been used to
link TEMPO-based alkoxyamine bearing a trichlorosilane group onto a magadiite
interlayer surface [56]. SI-NMP of styrene from the radical initiator immobilized on
magadiite occurred in a controlled manner. Moreover, the fine dispersion state of
magadiite in the PS matrix contributed to an increase in the thermal stability of PS.
2.4 NMP from Metal and Semiconductor Surfaces
As a result of their conduction properties, metallic surfaces are particularly

attractive materials. Jérôme and coworkers reported a two-step procedure to
Cathodic potential
+ + +
DMF, TEAP Styrene, BTE
n n
125°, toluene
O N O N
O O O O
m
O N
O O
Scheme 17 Two-step grafting-from strategy using electrochemistry
functionalize steel with polymer brushes [57]. The electrografting of an inimer to an

acrylate bearing a TEMPO-based alkoxyamine moiety on the ester group was used
for the preparation of polyacrylate brushes. After the electrografting process,
SI-NMP of styrene was performed in the presence of a free-radical initiator
(Scheme 17). Grafted PS chains were removed from the surface under acidic
hydrolysis. The restored metal substrate was then used for further electrochemical
reactions. A similar procedure was also applied to stainless steel surfaces [58]. To
this end, the electrografting of poly[2-phenyl-2-(2,2,6,6-tetramethylpiperidin-1-
yloxy)-ethyl acrylate] (PPTEA) onto stainless steel was first carried out and then
followed by the NMP of 2-(dimethylamino ethyl)acrylate and styrene or n-butyl
acrylate, initiated from the electrografted polyacrylate chains in the presence of a
TIPNO-based alkoxyamine. In order to impart antibacterial properties to the
obtained materials, quaternization of the grafted copolymers was then performed.
Jérôme and coworkers also reported an electrochemical approach based on the
simultaneous electrodeposition of silver and the electrografting of polymer chains
grafted onto stainless steel and used as a cathode [59]. This strategy allowed the
synthesis of poly(ethyl acrylate), PPTEA, and poly(8-quinolinyl acrylate). Hence,
silver-immobilized polymer films having antibacterial properties were efficiently
prepared in a single step.
A colored polymer/aluminum hybrid pigment was synthesized by NMP initiated
from the surface of aluminum flakes [60]. The latter were coated with a thin silica
layer. In this case, the chemical grafting of the initiator was performed through
silylation reactions. The initiator used was an SG1-based alkoxyamine
functionalized with an alkoxysilane moiety. This compound was previously pre-
pared from the intermolecular radical 1,2-addition of Blocbuilder MA in the
presence of 3-(trimethoxysilyl)propyl acrylate. Styrene or n-butyl acrylate were
then copolymerized with vinyl dye monomer in a controlled manner.
Many reports related to SI-CRP on metal describe the use of gold nanoparticles
and mainly from SI-ATRP. We note only one report describing the modification of
gold nanoparticles with SI-NMP. In this report, the NMP initiator was a TEMPO-
derivative functionalized with disulfide as ligand for the synthesis of gold
nanoparticles [61]. Two populations of gold nanoparticles, of 1.5 and 5.5 nm
diameter, covered with PS of 10,000 g mol1 were prepared.
Similarly, CdSe nanoparticles have been functionalized using ligand exchange
reactions [62]. The nanoparticles were stabilized by the tri-n-octylphosphine oxide
ligand. TEMPO-based alkoxyamines containing phosphine groups were introduced

to CdSe nanoparticles following a ligand-exchange strategy. First, the tri-n-
octylphosphine oxide ligand was replaced with pyridine, followed by exchange
with the appropriate alkoxyamine. From the surface of functionalized CdSe
nanoparticles, PS and poly(styrene-co-MMA) copolymers were efficiently
obtained.
2.5 NMP from Carbon Surfaces
Carbon-based materials have attracted wide interest in the materials science com-
munity for decades. These materials are extremely light and versatile. Indeed,
depending on the local bonding of the constituting carbon atoms, their properties
can be easily tuned. Diamond, carbon black, and graphite are well-known examples
of carbon-based materials; more recently discovered allotropes are fullerenes,
carbon nanotubes (CNTs), and graphene. Of these carbon-based materials, CNTs
are particularly studied because of their unique electronic, mechanical, thermal, and
chemical properties. To target specific applications, a number of experiments have
focused on the chemical modification of CNTs [63], including the use of CRP
techniques [64]. SI-NMP involves first attaching either an alkoxyamine moiety or a
nitroxide to the CNT surfaces, or the in situ synthesis of an alkoxyamine.
In order to facilitate anchoring of an initiator at the surface of CNTs (and carbon
in general), these substrates first need to be treated. For instance, carboxylic acid
groups can be introduced to single-walled nanotubes (SWNTs) and multiwalled
carbon nanotubes (MWNTs) by oxidation of the pristine nanotubes in the presence
of HNO3 or H2SO4/HNO3. The corresponding acid chloride derivatives are then
obtained by action of thionyl chloride in the presence of carboxylic acid-
functionalized CNTs. Introduction of the initiator/controller agent is finally
performed by esterification of 4-hydroxy TEMPO [65] or TEMPO-based
alkoxyamine bearing a hydroxyl group with acid chloride-functionalized CNTs
[66–68] (Scheme 18). Conventional radical polymerization of styrene, initiated by
AIBN or simple heating, in the presence of nitroxide-carrying CNTs provided
CNT–PS conjugates [65]. CNTs functionalized with TEMPO-based alkoxyamine
17 were used to perform SI-NMP of different monomers such as styrene,
4-vinylpyridine, and styrene sulfonate (SS). The resulting MWCNT–PS and
MWCNT–PS-b-P4VP exhibited relatively good dispersibility in various organic
solvents [66], whereas MWCNT–P4VP presented good dispersibility in acidic
aqueous solutions. MWCNT–PSS composites afforded stable dispersions in aque-
ous solutions over a large pH range [67]. In addition, SI-NMP of butyl acrylate and
N,N-dimethylacetoacetamide (DMAAm) were also successfully performed from
CNTs [69].
In addition to the modification of oxidized CNTs, another strategy consists in
performing radical addition reactions onto the carbon–carbon double bond of
CNTs, allowing introduction of specific groups able to initiate or mediate
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"You may guess what it is, if you like," said Forbes, "but it
would spoil all the fun to show it to you beforehand. Ask me
questions, and I'll answer yes or no."
"Well then, is it heavy?"
"Light?"
"Rather, yes."
"Can I hold it in my hand?"
"Yes."
"Is it long and straight?"
"It's quite straight—particularly so—and rather long."
"I say Forbes—it isn't—no it can't be a walking stick, of

course," said Jack growing excited, and fervently hoping it
was.
"No, but that's not a fair question, you must find out more
about it."
"Is it a useful thing?"
"Decidedly."
"Not too useful I hope," said Jack, somewhat dejectedly.
"I don't know what you mean by too useful—nothing can be

too useful."
"I mean it has nothing to do with lessons—a blotting book,

or slate, or anything of that sort."
"Well yes, it is something of that sort, but I know you
haven't got one, and really want one, I heard you ask
Geoffrey for his only the other day."
"It's a ruler!" said Jack blankly.
"Yes—but not only a ruler. Here, I'll let you feel it, old boy."
Jack felt it.
"It's one of those rulers with a pencil in it," he murmured,

then he added effusively lest Forbes should think him
ungrateful, "thanks awfully, it's jolly, it's awfully kind of
you."
Forbes felt and saw his little brother was disappointed.
"I quite forgot you didn't care for useful things, I like them
myself. But," he added, anxious to raise Jack's spirits, and
to make the best of his present which he felt was a failure,
and unappreciated, "this is a particularly nice ruler—it has a
first-rate pencil in it, and a view of the Grammar School and
Arboretum outside. That's why I got it, I thought you'd be
sure to like it."
"Forbes," said Mr. Hodson, laying a kind hand on the boy's
shoulder,
"you remind me of a verse in Proverbs, 'He that ruleth
his spirit is greater than he that taketh a city.'"
"Thanks awfully," was all that Jack could think of to say,
then after a moment's pause he asked, "What are you going
to give Geoff?"
"I'm giving him a walking stick, a regular wopper. I got it

while you and he were looking after the doll. It has a knob
at the end the size of my fist. I've asked them to send it out
to Hazelbury for me, as I was afraid Geoff would see me
carrying it."
"I say Forbes," said Jack colouring, and in a low voice, "you
wouldn't, I suppose, give Geoff the ruler and let me have
the stick?"
"No, certainly not," said Forbes angrily. "You are an

ungrateful sneaking little scamp, get away with you."
Jack burst into tears at this, and ran past Mr. Hodson and
Geoff, who had overheard Forbes' words, as he had raised
his voice in his anger.
Mr. Hodson turned round and looked at Forbes. The light of

a lamp close by shewed him the indignant light in the boy's
eyes.
"He's gone to complain to nurse now I suppose," he said,

angrily looking after Jack's little figure, as he ran crying up
the drive and into the house.
"Forbes," said Mr. Hodson, laying a kind hand on the boy's

shoulder, "you remind me of a verse in Proverbs, 'He that
ruleth his spirit is greater than he that taketh a city.' You
have the chance of being a greater man then even
Alexander—for though he conquered the world, he could not
conquer his own temper, and killed his best friend in a fit of
anger."
"Thank you Sir," said Forbes, "I'll remember."
CHAPTER IV.
TAKING A CITY.
Geoffrey remembered Mr. Hodson's words later in the

evening.
He did not turn in at the garden gate with Forbes, but

telling him he had some business to do before going in to
tea, he gave his presents into his brother's keeping, and ran
down the hill on the summit of which their house stood.
At the bottom of the hill, he came upon a tumbled-down

cottage, standing quite by itself. Old Rachel, of whom Mrs.
Green had told them, lived here.
The thought of Rachel had lain very heavily on Geoffrey's

heart the last two or three days. He could not forget that
she was a mother, and a mother neglected by her only
child, who, when she gave her anything at all, only passed
on to her what she couldn't eat herself. He was thinking of
Rachel when the apple puffs were passed round at dinner.
Now apple puffs was a favourite dish of Geoffrey's, as I
fancy it is of most boys. They looked particularly tempting
to-day, and he ate the first with a relish. It was just as he
was taking his second, that Mrs. Green's words came across
his mind, "and if ever she gives her anything, you may be
quite sure it ain't fit to eat, something they can't eat
themselves because it's turned."
Geoffrey looked at the puff as it lay so invitingly on his

plate. It was three cornered, and a little burnt at the edges,
which made it all the nicer in Geoffrey's opinion, and a nice
layer of white sugar lay on the top.
How good it looked! For a moment the boy gazed at it

undecidedly, then, when no one was looking, he put it into
his jacket pocket, and resolved to take it round to old
Rachel when they came back from Ipswich.
"For once," thought Geoff, "she shall have something that

somebody else wants."
He had had some difficulty in knowing how to stow away his

many presents so as not to crush his apple puff, but he had
managed somehow, and now as he stood outside the door
of Rachel's cottage, he took the puff out and was glad to
find it still whole. It certainly looked very tempting, and
Geoffrey was hungry after his walk. No one would see if
after all he ate it, instead of giving it to old Rachel, and no
one would consciously miss it.
For a moment the boy's resolution wavered, then he

knocked at the door.
Now an apple puff was not a very great thing to give up for
the sake of another, and perhaps some of my little readers
may think that it would not have signified very much if
Geoffrey had eaten it after all. But we must remember, that
life is made up of little things, and the great battle of life,
on which so much depends, consists often of little victories
and little losses, and this small victory that Geoffrey gained
that afternoon helped him in after years to gain a far
greater one.
When he grew up to be a man, there was something he

wanted very much, which was far more worth having than
this apple puff. He wanted it so much that he sometimes
felt he would almost give his life to possess it for ever such
a short time; but somebody else wanted it too, someone
who was weaker than he was, and who perhaps needed it
more than he did, and Geoffrey gave it right up for the sake
of that other.
I do not think he would have acted so nobly when he was a

man, if he had not begun quite early in life to deny himself.
If he had lost this little battle and had eaten the apple puff
outside old Rachel's door, in all probability he would have
lost that greater battle in after life.
"You are old Rachel, aren't you?" asked Geoffrey.
"Well, what if I be?" she answered.
"Come in," said a quavering voice as Geoffrey knocked, and
on entering, he saw a haggard looking old woman, with a
forbidding expression of face, and grey straggling hair,
crouching over a small fire.
"You are old Rachel, aren't you?" asked Geoffrey, who had
never seen her before.
"Well, what if I be?" she answered in a low gruff voice, "I

don't want no one to come interfering with me, leastways a
child. What do you want—eh?"
"I've brought you an apple puff," said Geoffrey, standing

still by the door.
"Shut the door, can't ye," said Rachel shivering, "the

draught's enough to cut one in two. An apple puff is it? That
ain't the kind of food I want, I ought to be fed on arrowroot
I tell ye, and sweet puddings and the like. But Jane never
sends me what I need, it's either somethin' that's turned
bad, or else what I can't eat."
"This is quite new and fresh," said Geoffrey, shutting the

door and coming a little nearer, while he laid the puff on the
table, "perhaps you've never tasted a puff—it's awfully good
—I wish you'd try it."
"That's a likely story, if Jane sent it," said Rachel glancing at

it, and then looking up suspiciously at Geoffrey.
"No one sent it," interposed Geoffrey. "We had them for
dinner to-day, and I thought you'd like one as they were so
good. I'm Geoffrey Fortescue, and I heard of you from Mrs.
Green."
Rachel looked back again at the fire, muttering to herself,

and Geoffrey looked round the room, and thought how bare
it was, and how lonely Rachel looked.
"Haven't you any money to get things with?" he asked.
"Money ain't for such as me: the big folk that don't need it,
they have the money. This world's comforts ain't for me."
"There's Heaven for you," said Geoffrey.
Rachel darted a quick look at the boy, and as she saw the
earnest young face looking at her so pitifully, the expression
on her own face softened, and she shook her head.
"I take it Heaven is a long way off," she said sadly.
"It doesn't seem so very far," answered Geoff, "Mother is

there, and I sometimes feel she's quite close."
"Heaven ain't meant for such as me," muttered Rachel,

cowering closer to the fire.
"I thought God loved everybody, and meant Heaven for the
whole world," said Geoff, "and," he added earnestly, "I'm
quite sure God must want you there, because you are so
lonely."
Rachel wiped away a tear or two with her apron. She had
not cried for many a long day. She had harboured too bitter
thoughts to allow of tears, but to-day, something in the
boy's simple words touched her hard old heart.
"I mustn't stop," said Geoffrey, looking out of the window at

the darkness, "or Nurse won't like it. But I'll ask Mr. Hodson
to come and see you, and I'll leave the apple puff, for it's
ever so good, if you'll only try it."
Rachel nodded her assent to the last sentence, but added:

"But don't you bring no parsons to see me. I don't want no
parsons here, unless," she added with a sob, and beginning
to rock herself backwards and forwards, "unless he can tell
me the way straight and plain to Heaven. I'd like to know
that."
Closing the door softly after him, Geoffrey ran as fast as he

could to Mr. Hodson. Although he ran the risk of a scolding
from Nurse for being late, he felt that Rachel must not be
left in her misery.
He arrived at the house nearly breathless, and told his

friend what had happened.
Mr. Hodson, who had together with the Vicar for many a
year tried in vain to overcome Rachel's objection to see a
clergyman, was glad enough of the news Geoffrey brought
him, and prepared at once to go and see her.
"Mr. Hodson," said Geoffrey anxiously, "God loves her,

doesn't He? And He won't turn her away from Heaven, if
she asks to be let in."
"If Rachel really wants to find God, He certainly will not turn
her away," answered Mr. Hodson. "The Lord Jesus Christ has
made a way there for us all, and old Rachel's way is the
same as yours and mine. Do you remember the story
Geoff," he added, as he put On his coat to start off at once,
"of the man who saved his children by making a bridge of
his own body from the window of his burning house to that
of the opposite one? The houses were very near together,
and he could reach from one window to another."
"His children one by one crossed over his body into safety,
and just as the last child was saved, the house fell in, and
the man was killed. When the Blessed Lord Jesus died on
the Cross, He made a bridge for Rachel, and for you and for
me to Heaven. You see, I have good news for your old
friend, Geoff my boy, so you run home as fast as you can or
you'll get a scolding."
And Geoff did get a scolding. Nurse met him at the door.
"Master Geoff," she cried, "I'm downright ashamed of you

for setting the children such an example. There I've been
worrying after you for the last twenty minutes, and thought
you'd come to some accident or other. I'm downright
ashamed of you."
"I had some business to do," said Geoffrey, trying to pass

her. But Nurse placed her portly figure in his way.
"Business! A chit like you talking of business! What'll you

come to next, I wonder. You're a naughty boy and ought to
be ashamed of yourself. What business have you had to do,
I should like to know, except to be a good obedient boy.
That's the business you ought to be doing I take it."
Geoffrey flushed angrily. His mother never scolded him in

this way, and he had often run messages for her as late as
this by himself.
"Let me pass, Nurse," he said angrily, trying to push past

her, "I've not been doing anything wrong."
"Nothing wrong!" exclaimed Nurse, catching hold of his

arm. "Nothing wrong to make me that anxious about you
that I didn't know what to do—nothing wrong that you've
kept us all waiting for tea, and have set a bad example to
all the children. I'm ashamed of you Master Geoff. Now I
should like to know what you've been about, and I mean to
know too."
But at the sight of the bread and water, he lost his temper
completely,
and taking up the glass, he threw it on to the ground.
Now Geoff did not wish to tell Nurse about the apple puff,
and felt exceedingly angry at being treated like a little boy,
and held by the arm in this way. So raising his hand he
struck nurse's arm as hard as he could, and then pale with
anger, he rushed into his bedroom and locked the door.
"Well I never!" ejaculated nurse. "If that isn't a wicked

temper, I don't know what is."
When she went back into the nursery a few minutes

afterwards, she informed the children that Geoff had been a
naughty boy, and was to have no tea that evening, but that
Forbes might put a glass of water and some bread outside
his door, but was not to speak a word to him.
Forbes, in utter astonishment at his elder brother being

punished in this way, obeyed wonderingly.
Now it was a great pity that Geoffrey had not at once

explained to nurse the cause of his absence. She might
have given him a slight scolding, for not asking her leave
before going, but her kind heart would have sympathized
with him, in his wish to do a kindness.
But Geoffrey's pride had stood in the way. He could not

endure being treated like a little boy, and scolded like a
naughty child, and as he paced up and down his room, his
indignation rose, and reached its climax when he heard
Forbes' footstep outside, and the sound of him quietly
laying down his tea, as he supposed, by his door without a
word. Was he to be treated then like a mere baby? And to
be held in disgrace like Jack or Dodie would have been, if
they had been naughty?
He opened his door impatiently to call after Forbes to take

away his tea, but at the sight of the bread and water, he
lost his temper completely, and taking up the glass, he
threw it on to the ground, smashing it to pieces. Then
locked his door again, and would not open it, though nurse
shook it violently.
Then it was that Mr. Hodson's words about Alexander came

into his mind, and Geoffrey stood quite still in his walk.
"'He that ruleth his spirit is greater than he that taketh a

city,'" thought Geoff.
Half an hour afterwards, to Forbes' intense astonishment,

Geoffrey appeared in the nursery and apologized to nurse.
Nurse said nothing, but going to the cupboard, she mixed

some gregory powder in a wineglass, saying, "anyone who
shows temper like that, I take it, must be ill. There my
dear," she added kindly, "you drink that, there's a good boy
—and you'll feel better to-morrow."
And Geoff drank it to the dregs, and in so doing was greater

than Alexander the Great.
CHAPTER V.
"POOR LITTLE LAD."
Geoffrey could not fail to acknowledge to himself that after

all, Nurse had been wise in putting Dodie into a frock with
high neck and long sleeves, for the winter was unusually
severe.
Snow lay for several days some inches thick in the garden,
and though the boys enjoyed the snowballing well enough,
and were able to keep themselves thoroughly warm, little
Dodie seemed to feel the cold very acutely, and often came
in from her daily walk crying from the pain of freezing
fingers.
In fact, the child did not seem herself, and Nurse began to
grow uneasy about her, particularly as in seven days' time,
Major Fortescue was expected and she was naturally
anxious that all the children should be looking their best on
his arrival.
In Geoffrey's eyes, Dodie seemed to be growing thinner and

smaller altogether, and a terrible fear seized him lest she
was going to be ill, and would be so when his Father
arrived.
As the days past, he gave up snowballing, and spent his
time in the nursery with Dodie, who was not allowed out.
"I think the cold has struck her," said Nurse, as one day she
altogether refused to eat her dinner. "I've a mind to send
for Dr. Booth, the powders I've been giving her don't seem
to be what she wants."
Geoffrey laid down his knife and fork, feeling a sudden

disinclination for the mutton and dumplings before him.
"Do you think Dodie is going to be ill?" he asked anxiously.
"I hope not, my dear, but it ain't like her to turn away from
her food, and she has a nasty little cough that don't get
better. Anyways I'll ask Dr. Booth to look in, there can't be
no harm in that. There, there my darling," she added,
taking Dodie on to her knee, "don't cry, there's a pet."
Nurse looked down at Dodie's little face which was lying on

her arm.
"I don't like the look of her," she murmured more to herself
than to anyone else, "her eyes are too bright to be natural,
and she's restless, poor little dear." Then louder she added,
"Geoff, you might run down when you've finished your
dinner and ask the doctor to be so good as to look in. You'd
catch him before he starts out on his rounds if you're
quick."
"Dr. Booth," he said,—looking up into the Doctor's face—
"will Dodie be well by the time Father comes home?"
Geoffrey, who had listened with a beating heart to all Nurse

had said, sprang up at once, and not heeding Nurse's
injunction to finish his dinner first, ran off at once for the
Doctor, and returned again in an incredibly short time.
To his excited imagination, the few minutes that elapsed

between leaving the message at the doctor's door and his
arrival seemed hours, and then at last his ring was heard,
and a minute after, he stood looking at Dodie, who still lay
in nurse's arms.
Geoff did not move his eyes from his face, till Nurse
suddenly looking up and becoming conscious of the three
little listeners who stood around, ordered them all
peremptorily out of the room. Geoffrey, however, waylaid
the Doctor as he left.
"Dr. Booth," he said, standing with his hands thrust deeply

in his pockets, and looking earnestly up into the Doctor's
face as he put on his coat in the hall, "will Dodie be well by
the time Father comes home?"
The Doctor shook his head somewhat ominously.
"That I can't tell you, my boy," he answered, as he buttoned

up his coat and smoothed his collar, "with care I hope your
little sister will get well before very long—but it will require
care—and I can't say exactly when she will be herself
again."
"Is she going to be very ill?" asked Geoff.
The doctor turned away somewhat hurriedly from the

anxious face looking up into his, and fidgeted a little
nervously with his hat before putting it on. Then clearing his
throat, he looked round again and patted the boy on the
head saying, kindly:
"Care and physic do wonderful things, my boy—for all I
know, your little sister will be having a game of snowballing
with you this day week."
"I do hope she'll be well by the time Father comes," said

Geoff with a sigh.
"Oh well—who knows!" said Dr. Booth jovially—and

ramming his hat on his head, he nodded to Geoff, and in a
minute more was driving away from the house, but not
away from the remembrance of those anxious eyes that had
been raised so beseechingly to him,—which remembrance
made him shake his head, murmuring "poor little lad."
When Geoff went up to the nursery, he saw Nurse had been

crying, but when he asked what the Doctor really thought of
Dodie, she told him she had no time to talk and that he had
better go down to the other boys in the schoolroom as
Dodie had to go straight to bed, and mustn't be disturbed
by any noise.
Geoffrey did as he was bid, but with a heavy heart, feeling

quite sure that Nurse's tears meant that Dodie was very ill.
He could not play with Forbes and Jack, or even read, but
sat by the fire, looking silently at the red coals, for an hour
or more.
It was the greatest relief when Nurse at last came down and
told him he might go upstairs and watch by Dodie's crib
while she had her tea, and that was the beginning of a
continual watching on the boy's part. Nurse finding how
gentle and tender he was, and how noiselessly he could
move about when he liked, did not object to his spending
many hours by Dodie's crib, and indeed, in her great
anxiety, she began to be thankful for the boy's presence.
For the Doctor's report of Dodie had been serious. The child

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Controlled Radical Polymerization at

and from Solid Surfaces 1st Edition

Dynamic Chemical Processes on Solid Surfaces: Chemical

Solution and Surface Polymerization 1st Edition Eli

Atomic Scale Dynamics at Surfaces Theory and

Solid-Solid, Fluid-Solid, Fluid-Fluid Mixers 1st

Solid State Properties From Bulk to Nano 1st Edition

Theorising Media and Conflict 1st Edition Philipp Budka

Handbook of Self Cleaning Surfaces and Materials From

Food from the radical center Gary Paul Nabhan

Philipp Vana Editor

A. Abe, Yokohama, Kanagawa, Japan

More information about this series at http://www.springer.com/series/12

ISSN 0065-3195 ISSN 1436-5030 (electronic)

Library of Congress Control Number: 2015945965

Springer Cham Heidelberg New York Dordrecht London

Printed on acid-free paper

Springer International Publishing AG Switzerland is part of Springer Science+Business Media

Nitroxide-Mediated Polymerization from Surfaces . . . . . . . . . . . . . . . 1

Nitroxide-Mediated Polymerization from

Trang N.T. Phan, Jacques Jestin, and Didier Gigmes

Abstract The current chapter gives a general overview on surface-initiated

Keywords Grafted or brush polymers • Nitroxide-mediated polymerization •

T.N.T. Phan and D. Gigmes (*)

TEM Transmission electron microscopy

Scheme 2 Mechanism of nitroxide-mediated polymerization

Fig. 1 Structure of nitroxides frequently used for SI-NMP. TEMPO 2,2,6,6-tetramethylpi-

2.1 NMP from Silicon Oxide Surfaces

2.1.1 NMP from Silicon Oxide Planar Surfaces

macroalkoxyamines on the surface and nitroxide in solution allowed the controlled

EtO 4 (R=Me, X=H) 6 7

LB lithography for spatially controlled attachment of initiator to form regular

Scheme 7 Triethoxysilyl alkoxyamines derivatives of TEMPO 8, SG1 9, and TIPNO 10

Scheme 8 Synthesis of surface-grown styrene-based homopolymer and diblock copolymer

Recently, Studer and coworkers [19] prepared polymer brushes bearing

in the presence of SG1 as controlling agent (Scheme 9). Elaboration of block

2.1.2 NMP from Silicon Oxide Particle Surfaces

Conformation of Grafted Polymer Chains

2.1.3 NMP from Porous Silicon Oxide

In comparison with colloidal particles such as silica or planar surfaces such as

Scheme 11 Polymerization of styrene on metal oxide nanoparticles

2.2 NMP from Metal Oxide Surfaces

Scheme 12 Grafting-from of N-isopropyl acrylamide from the surface of γ-Fe2O3 nanoparticles

Scheme 13 Grafting-from strategy for preparation of well-defined PS-grafted magnetic γ-Fe2O3

Scheme 14 Process of poly(ionic liquid) growth at CuO surface

tert-butyl hydroperoxide. Polymerization of 1-(4-vinylbenzyl)-3-butylimidazo-

2.3 NMP from Clay Mineral Surfaces

consisted in attaching 2-methacryloyloxy ethyl trimethylammonium chloride to the

Scheme 16 SI-NMP of styrene from laponite clay platelets

microscopy (TEM) performed on these samples demonstrated a completely exfo-

2.4 NMP from Metal and Semiconductor Surfaces

As a result of their conduction properties, metallic surfaces are particularly

Scheme 17 Two-step grafting-from strategy using electrochemistry

functionalize steel with polymer brushes [57]. The electrografting of an inimer to an

ligand. TEMPO-based alkoxyamines containing phosphine groups were introduced

2.5 NMP from Carbon Surfaces

"Well then, is it heavy?"

"Can I hold it in my hand?"

"Is it long and straight?"

"It's quite straight—particularly so—and rather long."

"I say Forbes—it isn't—no it can't be a walking stick, of

"Is it a useful thing?"

"Not too useful I hope," said Jack, somewhat dejectedly.

"I don't know what you mean by too useful—nothing can be