Macromolecular

Rapid Communications Communication

Photoinduced Atom Transfer Radical

Polymerization Using Semiconductor
Nanoparticles
Sajjad Dadashi-Silab Mehmet Atilla Tasdelen, Abdullah Mohamed Asiri,
Sher Bahadar Khan, Yusuf Yagci*

Photoinduced atom transfer radical polymerization of methyl methacrylate initiated by in

situ generation of copper (I) complex from higher oxidation state species using neat zinc oxide
and iron-doped zinc oxide nanoparticles is investigated. The polymerizations proceed in a
well-controlled manner under UV light at room temperature
as evidenced by kinetic and light on–off experiments. The
evolution of molecular weight with conversion shows good
correlations between experimental and theoretical molecular
weights, which confirmed good control over polymerization
along with a narrow molecular weight distribution.

1. Introduction control is established by maintaining the dynamic equilib-

Controlled/living polymerization (CLRP) techniques pro-
vide the possibility of synthesis of well-defined polymers
with predetermined molecular weights (Mn) and narrow
molecular weight distribution (Mw/Mn), and controlled
molecular architecture.[1] Unlike to ionic polymerizations,
C/LRP methods improved tolerance to functional groups
and impurities, an expanded range of polymerizable mon-
omers, and an efficient means of copolymerizing a variety
of monomers. Among the various C/LRP methods, such as
atom transfer radical polymerization (ATRP),[2] reversible
addition–fragmentation chain transfer polymerization
(RAFT),[3] and nitroxide-mediated radical polymerization
(NMRP),[4] ATRP has achieved most research interests due
to its chemically versatility. In all these C/LRP methods,
S. Dadashi-Silab, Dr. M. A. Tasdelen, Prof. Y. Yagci
Department of Chemistry, Istanbul Technical University,
Maslak, 34469, Istanbul, Turkey
E-mail: yusuf@itu.edu.tr
Dr. M. A. Tasdelen
Department of Polymer Engineering, Faculty of Engineering,
Yalova University, 77100 Yalova, Turkey
Prof. A. M. Asiri, Dr. S. B. Khan, Prof. Y. Yagci
Center of Excellence for Advanced Materials Research
(CEAMR), Department of Chemistry, Faculty of Science, King
Abdulaziz University, Jeddah, Saudi Arabia
rium between the active and dormant species via a revers-
ible deactivation mechanism.
In recent years, the ATRP process has been improved by
externally applied stimulus polymerizations, such as acti-
vators generated by electron transfer (AGET),[5] activators
regenerated by electron transfer (ARGET),[5b,6] initiators for
continuous activator regeneration (ICAR),[7] supplementary
activator and reducing agent (SARA) ATRP,[8] electrochemi-
cally mediated ATRP (eATRP),[9] and photochemically medi-
ated ATRP.[10] Common feature of these systems is the in
situ generation of activator CuI by reducing of deactivator
CuII, and as a consequence capability to overcome some
drawbacks in conventional ATRP such as large amounts of
metal catalyst requirements and their oxidation.[11]
Semiconductor nanoparticles (NPs) are widely used
for degradation of toxic pollutants and organic dyes by
using solar energy based on absorbing light by NPs and
releasing of their electron.[12] These inorganic NPs have
rarely been used to initiate the polymerization of vinyl
monomers under light.[13] In a recent work, the semicon-
ductor NPs (ZnO, TiO2, Fe2O3, SnO2, ZrO2, CdSe, or CdTe)
were reported to initiate free radical polymerization of
acrylamide to form nanoparticle-based hydrogels under
sunlight.[14] Moreover, commercial titanium oxide NPs
were used to reduce CuII to CuI in UV-induced surface-ini-
tiated ATRP to produce polymer brushes.[14]

Macromol. Rapid Commun. 2014, 35, 454−459

454 © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com DOI: 10.1002/marc.201300704

Photoinduced Atom Transfer Radical Polymerization Using Semiconductor Nanoparticles
As part of our continuing interest to develop photoin-
duced ATRP,[15] various initiating systems including con-
ventional ATRP, reverse ATRP, and SR & NI (Simultaneous
Reverse & Normal) ATRP were extensively studied.[10a-e,16]
Here, we report the first successful use of semiconducting
zinc oxide and iron-doped zinc oxide NPs in photoinduced
ATRP of methyl methacrylate (MMA). Various control
experiments were performed with different conditions to
support the proposed mechanism.
2. Experimental Section
2.1. Materials
MMA (99%; Aldrich) was purified by passing through a
basic alumina column to remove inhibitor. N,N,N′,N′′,N′′-
Pentamethyldiethylenetriamine (PMDETA, 99%; Aldrich) was dis-
tilled before use. Ethyl α-bromoisobutyrate (EBiB, 98%; Aldrich),
acetonitrile (CH3CN, 99.9%; Merck), copper (II) bromide (CuIIBr2,
99%; Acros), iron (III) nitrate nonahydrate (FeIII(NO3)3·9H2O,
98%; Aldrich), zinc (II) nitrate hexahydrate (ZnII(NO3)2·6H2O,
98%; Aldrich), and methanol (CH3OH, 99.9%; Merck) were used
as received without any further purification. All other chemi-
cals were of reagent grade, purchased from Aldrich and used as
received.
2.2. Synthesis of ZnO Nanoparticles
Zinc oxide NPs were synthesized by simple hydrothermal
method using the aqueous (DI water) mixtures of zinc chloride
and ammonium hydroxide as source materials.[17] In a typical
reaction process, ammonium hydroxide solution was added drop-
wise in 0.1 M zinc chloride solution made in 100.0 mL of DI water
under constant stirring. The addition of ammonium hydroxide
was stopped when the pH of the solution reached 10.2. The reac-
tion mixture was then continuously stirred for 1 more hour and
the resultant solution was then transferred into a Teflon-lined
autoclave and heated up to 150.0 °C for 3 h. After terminating
the reaction, the autoclave was allowed to cool at room tempera-
ture and finally white precipitates were obtained, which were
washed with methanol several times and dried at room tempera-
ture. The dried products were then calcined at 400 °C for 3 h and
characterized in detail in terms of their structural, optical, photo-
catalytic, and sensing properties.
2.3. Synthesis of Fe-Doped ZnO Nanoparticles
Iron (III) nitrate and zinc (II) nitrate (1:3) were totally liquefied at
ambient temperature and adjusted the pH of resulted solution
above 10.0 by dropwise addition of 0.2 M NaOH solution with
constant vigorous stirring. The resulted basic solution was stirred
overnight at 60 °C and centrifuged the precipitate at 2000 rpm. Dis-
carded the supernatant solution and saved the precipitate. Washed
precipitate with ethanol for three times and then allow them to dry
first at ambient temperature and then in oven at 60 °C. Grinded the
precipitate and stored in a clean, dry, and inert plastic vials.
Macromol. Rapid Commun. 2014, 35, 454−459
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2.4. Polymerization
MMA (2 mL, 18.6 mmol), PMDETA (58.2 μL, 0.279 mmol), CuIIBr2
(20.7 mg, 0.093 mmol), EBiB (13 μL, 0.093 mmol), acetonitrile
(0.5 mL, 9.57 mmol), and ZnO NPs (7.6 mg, 0.093 mmol) were
placed into a Schlenk tube, and the reaction mixture was degassed
by two freeze–pump–thaw cycles and left in vacuum. The mixture
was irradiated by a Rayonet photoreactor equipped with 18 lamps
(Philips 8 W BLB), emitting light nominally at 350 nm at room
temperature. The light intensity was 22 mW cm−2 as measured
by Delta Ohm model HD-9021 radiometer. The resulted polymers
were precipitated in methanol and then dried under vacuum.
Chain extension was performed employing with [MMA]0/
[PMMA-Br]0/[CuIIBr2]0/[PMDETA]0/[ZnO]0 = 400/1/1/3/1. A mac-
roinitiator prepared by photoinduced ATRP after 1 h, PMMA-
Br (Mn,GPC = 2000, Mw/Mn = 1.15; 0.18 g, 9.3 × 10−2 mmol), MMA
(4 mL, 37.2 mmol), PMDETA (5.8 μL, 2.8 × 10−3 mmol), and CuIIBr2
(20 mg, 9.3 × 10−2 mmol) were put into a Schlenk tube, and the
reaction mixture was degassed by three freeze–pump–thaw
cycles and left in vacuum. The mixture was irradiated under the
same experimental condition and the reaction was ceased after
7 h by opening the flask and precipitated in the methanol. Finally,
the obtained polymer was dried under reduced pressure (conver-
sion: 48%, Mn,GPC = 22 000, Mw/Mn = 1.22).
2.5. Characterizations
UV spectra were recorded on a Shimadzu UV-1601 spectrometer.
Gel permeation chromatography (GPC) measurements were per-
formed on a Viscotek GPCmax autosampler system consisting of a
pump, a Viscotek UV detector, and Viscotek, a differential refrac-
tive index (RI) detector with three ViscoGEL GPC columns (G2000H
HR, G3000H HR, and G4000H HR, 7.8 mm internal diameter, 300
mm length) in series. The effective molecular weight ranges were
456−42 800, 1050−107 000, and 10 200−2 890 000, respectively.
THF was used as an eluent at flow rate of 1.0 mL min−1 at 30 °C.
Both detectors were calibrated with polystyrene standards having
narrow molecular weight distribution. Data were analyzed using
Viscotek OmniSEC Omni-01 software. 1H NMR spectra were
recorded on an Agilent NMR System VNMRS 500 spectrometer at
room temperature in CDCl3 with Si(CH3)4 as an internal standard.
The surface morphology of the NPs was studied using a JEOL
Scanning Electron Microscope (JSM-7600F, Japan). X-ray diffrac-
tion (XRD) patterns were taken with a computer controlled X’Pert
Explorer, PANalytical diffractometer.
3. Results and Discussion
Semiconductor NPs less than 100 nm in diameter, for
example, are optically clear (transparent in visible light)
but absorb light in the UV range and are being used as
photoinitiators for the free radical polymerization. These
NPs attract considerable attention due to their intrinsically
negligible light scattering, great specific surface area, mani-
festation of quantum confinement effects, and so on. Fur-
thermore, their light absorption maximum can be shifted
into a desired wavelength range by doping with other
455
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Rapid Communications S. Dadashi-Silab et al.

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(Fe/ZnO) NPs in the UV–Vis range have been examined by

Scheme 1. General mechanism of free radical photopo-
lymerization of vinyl monomers using ZnO semiconductors as
photoinitiator.
metals. For the photoinitiation of the polymerization of vinyl
monomers by zinc oxide NPs in the presence of water, the
mechanism presented in Scheme 1 has been reported. Upon
the photoexcitation of zinc oxide NPs, a positive hole (h+)
and an electron (e−) are generated in conduction and valence
bands correspondingly. Holes, photogenerated in ZnO
valence bands, can be reduced by either monomer or solvent
molecules leading to the formation of radicals, which react
with the monomers and initiate thereby polymerization.
On the other hand, direct electron transfer from the con-
duction band of ZnO NPs to monomer is also possible. Both
photogenerated electrons and holes induce the formation of
radicals, which are responsible for chain initiation.[18]
Well-crystalline ZnO and Fe/ZnO NPs were synthesized
in large quantity via simple hydrothermal and precipita-
tion processes. FESEM images show that both ZnO and Fe/
ZnO are grown in the form of spherical nanoparticles with
average diameter of 50 and 20 nm, respectively (Figure S1,
Supporting Information). The crystallinity and crystal
structure of the as-grown nanoparticles were evaluated
by XRD spectroscopy and the XRD spectrum is shown in
Figure S2 (Supporting Information). Both ZnO and Fe/ZnO
NPs exhibited identical peaks as that of Wurtzite hex-
agonal ZnO NPs, whereas Fe/ZnO NPs have a small shift
toward low two theta, which might be due to change in
lattice spacing of ZnO caused by Fe doping.[17,19] In order
to take advantage of the use of ZnO NPs in the poly-
merization, first, optical properties of reaction mixture
(MMA/CuIIBr2/PMDETA), ZnO, and iron-doped zinc oxide
UV–Vis spectroscopy. As shown in Figure S3 (Supporting
Information), at the irradiation wavelength only ZnO and
Fe/ZnO NPs absorb the light where the other components
of the reaction mixture are completely transparent.
Initially, the polymerization of MMA was exam-
ined by using the CuIIBr2/PMDETA as the catalyst, ethyl
α-bromoisobutyrate (EBiB) as the initiator, and ZnO NPs
as the photosensitive compound. During UV irradiation,
ZnO NPs easily absorb photons and promote electrons
from the valence bands to the conduction bands, and then
the excited electrons can spontaneously reduce CuIIBr2−
ligand to CuIBr−ligand, which operates the ATRP of MMA.
In order to confirm the initiating mechanism, various
control experiments including those in the absence
of nanoparticle, CuII or alkyl halide were conducted to
reveal the role of each component on the polymerization
(Table 1). When the polymerizations were conducted in
the absence of either ZnO NPs or alkyl halide or CuIIBr2,
the experiments failed to produce any polymer at the end
of irradiation and each component is required for suc-
cessful controlled radical polymerization. Polymerizations
proceed only when the redox components were present
in the system. Compared with neat ZnO NPs, Fe/ZnO NPs
provided relatively fast polymerization rate with narrow
molecular weight distribution (Table 1, entry 5). The
addition of Fe in ZnO increased the absorbance at higher
wavelengths as well as enhanced rate of polymerization
of the system. Previously, Fe-doped ZnO NPs showed
higher photocatalytic efficiency for dye degradation than
bare ZnO NPs at the same time of illumination.[20]
On the basis of the above results, the kinetic plot and
the evolution of molecular weight and distribution with
conversion for the photoinduced ATRP of MMA in the pres-
ence of ZnO (Figure 1) or Fe/ZnO (Figure 2) NPs were inves-
tigated. In both cases, the linear relationship between
monomer consumption, ln([M]0/[M]) with polymerization
time indicated that the propagating radical concentra-
tions were almost constant during the polymerization.

Table 1. The results of photoinduced ATRP of methyl methacrylate using ZnO and Fe/ZnO nanoparticles as photocatalyst.

Runa) [M]0/[RX]0/ NPs type Conv.b) Mn,thc) Mn,GPCd) Mw/Mnd)

[CuII]0/[L]0/ [%] [g mol−1] [g mol−1]
[ZnO]
1 200/1/1/3/0 – – – – –
2 200/0/1/3/1 ZnO – – – –
3 200/1/0/3/1 ZnO – – – –
4 200/1/1/3/1 ZnO 40 8000 8100 1.23
5 200/1/1/3/1 Fe/ZnO 57 11 400 11 900 1.18
a)The samples were irradiated under UV light (350 nm), time = 3 h; b)Measured gravimetrically; c)M
n,th = [M]0/[RX]0 × Mw,mon ×
Conv.; d)Number-average molecular weight (Mn,GPC) and molecular weight distribution (Mw/Mn) were determined by gel
permeation chromatography.

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 Macromolecular
Photoinduced Atom Transfer Radical Polymerization Using Semiconductor Nanoparticles Rapid Communications
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Figure 1. Photoinduced ATRP of MMA with [MMA]0/[RX]0/[MtX]0/[L]0/[ZnO]0 = 200/1/1/3/1 ratio a) kinetic plot and b) molecular weights
and distributions of the resulting polymers as a function of degree of conversion.

Evolution of the molar mass (Mn) and molecular weight
distribution (Mw/Mn) (Figures 1b and 2b) show that
during photoinduced ATRP of MMA with [MMA]0/[RX]0/
[MtX]0/[L]0/[ZnO]0 = 200/1/1/3/1 ratio, the polydispersity
indexes in both cases were slightly broader (1.18−1.30),
and the obtained molar masses were in good agree-
ment with the theoretical values, indicating high initia-
tion efficiency. Notably, Fe/ZnO NPs allow a much faster
ATRP and narrow polydispersity indexes over the polymer
properties than ZnO NPs.
GPC traces of the obtained polymers by ZnO and Fe/
ZnO NPs at different time intervals are presented in
Figure 3. It can be seen that the molecular weight of the
polymers shifted toward the higher molecular weight
region as the polymerization proceeded, indicating the
existence of controlled growing species in both cases.
To further investigate the effect of UV light irradiation
on the photoinduced polymerization of MMA, the light
was turned on and off intermittently during the reaction
(light off at 0–1, 2–3, and 4–5 h in Figure 4). First, mon-
omer, initiator, and catalyst were initially combined in
the absence of light and after 1 h, no polymerization was
observed. The reaction was then exposed to UV light for
1 h at room temperature, which resulted in approximately
13% monomer conversion. Thereafter, the light source was
periodically turned-off and the polymerization proceeded
at a much lower rate during this period, indicating a negli-
gible concentration of the active radical present under dark
conditions. Exposure to UV light for a second 1-h period
“turns” the polymerization back on and this “on”/“off”
cycle can be repeated numerous times with negligible
reaction in the absence of irradiation. The gradual increase
of the yield with the irradiation time clearly indicates that
the polymerization is driven by light. The polymer yield
increased only under the UV light irradiation, while the
polymerization stopped in the light-off period.
The living nature of the system was further examined
by treating the macroinitiator made by this technique
with a same monomer for chain extension using the
same conditions. For this purpose, a macroinitiator (Mn,GPC
= 2000 g mol−1, PDI = 1.15) prepared by photoinduced
ATRP was employed with [MMA]0/[PMMA-Br]0/[CuIIBr2]0/
[PMDETA]0/[ZnO]0 = 400/1/1/3/1 ratio in the chain exten-
sion reaction. Figure 5 shows the GPC analysis of the sam-
ples taken during the chain extension process before and
after sequential monomer addition. As shown in Figure 5,

Figure 2. Photoinduced ATRP of MMA with [MMA]0/[RX]0/[MtX]0/[L]0/[Fe/ZnO]0 = 200/1/1/3/1 ratio a) kinetic plot and b) molecular weights
and distributions of the resulting polymers as a function of degree of conversion.

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 Macromolecular
Rapid Communications S. Dadashi-Silab et al.

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Figure 3. Gel permeation chromatography (GPC) traces of the PMMAs using a) ZnO and b) Fe/ZnO nanoparticles as photocatalyst at dif-
ferent time intervals.

the polymer chains were clearly shifted to higher mole-

cular weights (Mn,GPC = 22 000 g mol−1, PDI = 1.22) and no
detectable amount of unreacted initial block. Figure S4
(Supporting Information) shows a typical 1H NMR spec-
trum of obtained PMMA homopolymer. A strong peak
at 3.62 ppm (Figure S4a, Supporting Information) was
assignable to the methoxy protons of PMMA. The small
peak at 4.0 ppm (Figure S4g, Supporting Information) was
assignable to the methylene protons of the initiator. The
results of 1H NMR analysis and chain extension demon-
strated that well-defined PMMA bearing a halide group
was synthesized via photoinduced ATRP.
A possible mechanism for the polymerization should
consider continuous regeneration of copper catalyst in
an activator generated by electron transfer (AGET) ATRP
mechanism as illustrated in Scheme 2. The primary

Figure 5. GPC analysis of the samples during the chain extension

process before (black line) and after (red line) sequential mon-
omer addition.

photochemical reaction involves the generation of a

Figure 4. Effect of UV light during the polymerization of MMA at
room temperature; [MMA]0/[RX]0/[MtX]0/[L]0/[ZnO]0 = 200/1/1/3/1.
positive hole (h+) and an electron (e−), which are gener-
ated in conduction and valence bands, correspondingly.
The valence band electrons reduced the CuII/L to CuI/L
directly,[14] which was used as activator in the AGETATRP.
Subsequently, polymerization was started by the activa-
tion of an R–X initiator by the CuI/L activator. Notably,
each component of the system including ZnO NPs or alkyl
halide or CuIIBr2 or light irradiation is required for suc-
cessful controlled radical polymerization.

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Photoinduced Atom Transfer Radical Polymerization Using Semiconductor Nanoparticles
Scheme 2. Proposed mechanism of photoinduced ATRP of MMA
using semiconductor ZnO nanoparticles.
4. Conclusions
We report the use of ZnO and Fe/ZnO as photocatalyst
for photoinduced ATRP of MMA in the presence of CuII/
PMDETA system. The molecular weights of obtained poly-
mers and their distribution are well controlled. The growth
of polymer chains can be manipulated by switching on/
off the UV light. Compared with neat ZnO NPs, Fe/ZnO NPs
provides relatively fast polymerization rate with narrow
molecular weight distribution. Attractive features of this
system include no use of expensive compounds, metals,
and conventional radical initiators.
Supporting Information
Supporting Information is available from the Wiley Online
Library or from the author.
Received: September 10, 2013; Revised: October 28, 2013; Published
online: November 26, 2013; DOI: 10.1002/marc.201300704
Keywords: atom transfer radical polymerization (ATRP); metal-
organic catalysts/organometallic catalysts; photochemistry;
photopolymerization; semiconductor nanoparticles; zinc oxides
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