In-situ photoinduced formation of self–assembled Ag NPs using POSS-TX as nano-photoinitiator in PEGMEA/PEGDA polymer matrix and creating self-wrinkled pattern

Article abstract of DOI:10.1016/j.jphotochem.2018.03.024

Thioxanthone (TX) and its derivatives are playing an important role as photoinitiators for photopolymerizable formulations. But another significant role of the photoinitiators was recently discovered, namely, the photoreduction of metal salts to metal nanoparticles, in which mainly ketyl radicals were responsible for this process. Functionalization of Polyhedral Oligomeric Silsesquioxanes (POSS) with TX is reported here and used for simultaneous preparation of self-assembled silver nanoparticles (Ag NPs) with POSS cage and polymer matrix. Covalent attachment of POSS-TX to the polymer matrix resulted in self-assembled Ag NPs in a self-wrinkled pattern.

Full text of DOI:10.1016/j.jphotochem.2018.03.024

Accepted Manuscript
Title: In-Situ Photoinduced Formation of Self–Assembled Ag
NPs Using POSS-TX as Nano-Photoinitiator in
PEGMEA/PEGDA Polymer Matrix and Creating
Self-Wrinkled Pattern
Authors: Gonul S. Batibay, Omer Tahir Gunkara, Nuket Ocal,
Nergis Arsu
PII:
S1010-6030(17)31821-X
DOI:
Reference:
https://doi.org/10.1016/j.jphotochem.2018.03.024
JPC 11193
To appear in:
Journal of Photochemistry and Photobiology A: Chemistry
Received date:
Revised date:
Accepted date:
14-12-2017
15-3-2018
17-3-2018
Please cite this article as: Gonul S.Batibay, Omer Tahir Gunkara, Nuket Ocal,
Nergis Arsu, In-Situ Photoinduced Formation of Self–Assembled Ag NPs Using
POSS-TX as Nano-Photoinitiator in PEGMEA/PEGDA Polymer Matrix and
Creating Self-Wrinkled Pattern, Journal of Photochemistry and Photobiology A:
Chemistry https://doi.org/10.1016/j.jphotochem.2018.03.024
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In-Situ Photoinduced Formation of Self–Assembled Ag NPs Using POSS-
TX as Nano-Photoinitiator in PEGMEA/PEGDA Polymer Matrix and
Creating Self-Wrinkled Pattern
Gonul S. Batibay, Omer Tahir Gunkara, Nuket Ocal, Nergis Arsu*
Department of Chemistry, Yildiz Technical University, Davutpasa Campus Istanbul 34220,
Turkey
E-mail: narsu@yildiz.edu.tr
Graphical abstract
Highlights
 Thioxanthone chromophore attached to Amino POSS
 In-situ photosynthesis of silver nanoparticles achieved with TX-POSS
 Self-Wrinkled pattern obtained for UV-Cured polymeric films
Abstract
Thioxanthone (TX) and its derivatives are playing an important role as photoinitiators for
photopolymerizable formulations. But another significant role of the photoinitiators was
- 1 -

recently discovered, namely, the photoreduction of metal salts to metal nanoparticles, in
which mainly ketyl radicals were responsible for this process. Functionalization of Polyhedral
Oligomeric Silsesquioxanes (POSS) with TX is reported here and used for simultaneous
preparation of self-assembled silver nanoparticles (Ag NPs) with POSS cage and polymer
matrix. Covalent attachment of POSS-TX to the polymer matrix resulted in self-assembled Ag
NPs in a self-wrinkled pattern.
Keywords: photopolymerization, nanocomposites, Self–Assembled, silsesquioxane (POSS),
silver-nanoparticles
1. Introduction
Photopolymerization has wide range of commercial applications such as coatings, adhesives,
dental composites, inks, printing plates, and microelectronics [1-2]. The key ingredient in
these photopolymerization formulations is the photoinitiator [3]. Generally, Type I and Type
II photoinitiators are used for industrial applications [1, 3-7].
Thioxanthone photoinitiators can generally be classed as Type II photoinitiators. Recently,
syntheses of thioxanthone-based one-component Type II photoinitiators were reported such as
mercapto [8], acetic acid [9-12], and anthracene [13-15], and visible [16-23] and water
soluble [24, 25] derivatives. A good match of the absorption spectrum of the photoinitiator
with the light source is of major importance and most commercially used photoinitiators are
tailored to the near-UV spectral region. For these reasons, thioxanthone based photoinitiators
show one of the best light absorption properties in the near-UV spectral region and, therefore,
are widely used. There are several methods for preparation of nanocomposites. Among them,
photochemical methods are much more convenient for many reasons such as space selectivity,
convenience and speed [26].
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Fabrication of nanocomposite materials with a controlled structure is a key component for the
improvement of new technologies. Non covalent interactions such as hydrogen bonding,
acid/base proton transfer and specific electrostatic forces leads to self-assembly which is an
effective technique [27].
Chemical cross-linking or physical blending methods can be used for the preparation of POSS
containing polymer nanocomposites by incorporation of POSS into polymer matrices. Hence
nanometer size of POSS allows good incorporation into polymeric materials the unique
capability to reinforce polymers.
These hybrid organic–inorganic nanocomposites, possessing several attractive properties such
as enhancements in the modulus and melt strengths, higher thermal stability and glass
transition temperature, flame and heat resistance, and more importantly, these property
enhancements occur even with low POSS content [28].
POSS may be attributed to as a silica nanoparticle consisting of a silica cage core, as well as
other organic functional groups attached to the corners of the cage
Preparation of micro- or mesoporous materials is possible with the aid of the cubic topology
of the molecule, although it is geometrically difficult to link cubes through only their corners.
There is good relationship between the degree of porosity and the efficiency of
polymerization and the flexibility of the organic polymerizable group.
In this communication, we report the formation of self-assembled Ag NPs (~18-23 nm) with
distribution controlled using POSS-TX in PEGMEA/PEGDA polymer matrix resulting in a
self-wrinkled pattern.
2.
Experimental Section
2.1. Materials
Reactions were checked by TLC. UV light and KMnO4 were used for visualizations of the
chromatograms. Thiosalicylic acid (Aldrich), Sulfuric acid (99.8%, Aldrich), Phenoxyacetic
acid (Aldrich), N,N-Dimethylformamide (DMF, 99.5%, Merck), 1,4-Dioxane (for analysis,
- 3 -

Merck), Ethyl acetate (for analysis, Merck), n-Hexane (for analysis, Merck), Thionyl chloride
(Aldrich), Aminopropylisobutyl POSS (Hybrid Plastics), Magnesium sulfate (anhydrous for
analysis, Merck), AgNO3 (for analysis, Merck), and Hydrochloric acid (HCl, 10%, Merck)
were used as received. The solvents were dried by standard procedures. Basic alumina was
used for removal of stabilizers from Methyl methacrylate (MMA, 99%, Merck) and MMA
was used after removal of stabilizer. Poly(ethylene glycol) methyletheracrylate (PEGMEA,
Sigma-Aldrich, Mn=550), Poly(ethyleneglycol)diacrylate (PEGDA, Sigma-Aldrich, Mn=700)
were used as received. Conventional drying and distillation procedures were employed for
solvents which were supplied by Merck.
2.2. Instruments
All melting points were uncorrected and determined on a Gallenkamp digital thermometer.
UV-Vis spectra were taken on a Varian UV-Visible Carry 50 Spectrophotometer.
Fluorescence and phosphorescence spectrums were recorded on a Jobin Yvon-Horiba
Fluoromax-P. 13C and 1H NMR spectra were recorded on a Bruker Avance III 500 MHz NMR
spectrometer relative to tetramethylsilane, with coupling constant (J) values in Hertz (Hz).
Peak multiplicities are designated by the following abbreviations: s, singlet; d, doublet; dd,
double doublet; t, triplet; dt, double triplet; m, multiplet; br, broad; p, pentet; amd hept, heptet.
2.3. Synthesis and Characterization
2.3.1. Synthesis of 2-(carboxymethoxy)thioxanthone (TX-OCH2COOH) [29]:
Thiosalicylic acid (1.6 g, 10.3 mmol) was slowly added to concentrated sulfuric acid (15 mL)
and tihe mixture was stirred for 5 min to ensure through mixing. Phenoxyacetic acid (6.7 g, 44
mmol) was added slowly to the stirred mixture over a period of 30 min. After the addition, the
ο
reaction mixture was stirred at room temperature for 1 h, then at 80 C for 2 h, after which it
was left to stand at room temperature overnight. The resulting mixture was poured carefully
with stirring into a 10-fold excess of boiling water ant it was then further boiled for 5 min.
- 4 -

The solution was cooled and filtered. The residue was recrystallized from dioxane/water.
ο
Yield: 80%; mp: 200 C; IR (ATR): ν = 3480, 2927, 1753, 1637, 1603, 758; 1H NMR (250
MHz, DMSO-d6, δ): 8.46-7.42 (m, 7H, Ar H), 4.84 (s, 2H, CH2); C15H10O4S (286 g.mol-1):
Calcd. C 62.94, H 3.50, S 11.19; Found C 63.59, H 4.36, S 10.95.
2.3.2. Synthesis of 2-[(9-Oxo-9H-thioxanthen-2-yl)oxy]acetyl chloride (TX-OCH2COCl):
The TX-OCH2COOH (200mg, 0.7 mmol) and thionyl chloride (1mL, 14 mmol) were stirred
in a round bottom flask without any solvent under nitrogen atmosphere. The mixture was
stirred overnight at room temperature. The reaction was controlled by TLC.
After completion of reaction, the excess of thionyl chloride was evaporated under reduced
pressure. The compound TXOCH2COCl was obtained as a yellow solid and used in the next
reaction without any further purification [30]. Yield100%
2.3.3. Synthesis of 2-(9-Oxo-9H-thioxanthene-2-yloxy)-N-(3-silsesquioxanylpropyl)
acetamide:
A solution of TXOCH2COCl (152 mg, 0.5 mmol) in dry DMF (3 mL) was added to
o
aminopropyl isobutyl-POSS (437 mg, 0.5 mmol) in dry DMF (3 mL) at 50 C under nitrogen
atmosphere. The resulting mixture was stirred overnight. After cooling to room temperature,
brine (50 mL) was added, and the mixture was extracted with AcOEt. The organic phase was
extracted with 10% HCl (20 mL) to remove the excess of aminopropyl isobutyl POSS. The
aqueous layer was dried over MgSO4, filtered, and concentrated. The compound was obtained
as a yellow solid. Yield 90%; decompn p.: 180±2 ̊
C; 1H NMR (500 MHz, CDCl3, δ): 0.53 (dd,
J= 3.78; 9.45 Hz, 16H, CH2-Si), 0.88 (dd, J= 2.20; 6.62 Hz, 42H, CH3), 0.57-0.61 (m, 2H,
CH2), 1.77 (hept, 7H, CH), 2.86-2.91 (m, 1H, N-CH2), 4.76 (s, 1H, O-CH2), 7.36 (dd, J=
2.83; 8.82 Hz, 1H, Ar H), 7.44-7.49 (m, 2H, Ar H), 7.56-7.61 (m, 2H, Ar H), 7.85 (bd, J=
2.83 Hz, 1H, Ar H), 8.16 (brs, 1H, NH), 8.54 (d, J= 8.82 Hz, 1H, Ar H); 13C NMR (125 MHz,
CDCl3, δ): 9.3 (7xCH), 22.4 (7xCH3), 22.5 (7xCH3), 23.8 (CH2), 25.6 (8xCH2), 40.3 (N-CH2),
- 5 -

43.2 (O-CH2), 111.2 (Car), 123.1 (Car), 125.9 (Car), 127.1 (Car), 128.3 (Cq), 129.1 (Cq),
129.7 (Cq), 129.8 (Car), 131.9 (Car), 137.6 (Cq), 157.5 (Cq), 161.0 (Car), 174.4 (C=O), 179.6
(C=O).
2.4. Preparation of Ag Nanoparticles in DMF
POSS-TX (5 mg, 0.05% wt) initiating systems added on AgNO3 (40 mg, 0.4% wt) mixture
was dissolved in 25 mL DMF. This solution was irradiated by Hamamatsu Lightningcure LC8
device.
2.5. Preparation of Ag Nanoparticles and Nanocomposite Thin Films Through In-situ
Photopolymerization Method
A PEGMEA and PEGDA mixture was chosen as the polymer matrix for preparation of
nanocomposites containing Ag NPs. AgNO3 (40 mg, 4%wt) and POSS-TX (5 mg, 0.05% wt)
were dissolved in a few drops of DMF and added into mixture of PEGDA (191 mg, 19.1%wt)
and PEGMEA (764 mg, 76.4%wt). In order to make the metal salt well distributed, the final
formulation was mixed by ultrasonic probe in an ice bath for 5 min and degassed. Finally,
formulations were coated onto the glass/aluminum surface using roller-coater which is
suitable for the coating 40 m thickness and cured by the mini UV-Curing unit.
3. Results and Discussion
The POSS molecule is tethered to the eight organic groups surrounding its cage and is bonded
to the silicon vertices, seven of which are propyl and one of which is amino, which are used
for functionalization with TX (see Scheme 1).
The main idea for this study is based on photochemical preparation of self–assembled Ag NPs
using POSS-TX either in solution or in the polymer matrix. The structure of one-component
- 6 -

POSS-TX was thought to have a key role especially for the formation of Ag NPs containing
composite polymer films since no additional chemical, either co-initiator or photoinitiator,
was added to the formulation. Indeed, the major contribution comes from it being a unique
compound which serves two roles: one is the photoreduction of AgNO3 and the other,
simultaneously, the formation of a wrinkled polymer matrix, when formulation contains
monomer mixture (see SEM images). First of all, UV-Vis absorption spectroscopy, which is
very effective for recording Ag NP formation, was employed. In this method, in half an hour
of irradiation, a nice and very strong surface absorption plasmon band appeared for Ag NPs
from POSS-TX and AgNO3 in DMF solution in air atmosphere, as given in Figure 1.
The nice colour change from yellow to reddish brown of POSS-TX/DMF solution was also
good proof of formation of Ag NPs, as well as the very strong SPR absorption band belonging
to the Ag NPs which appeared at 450 nm with a nice shape. This change of colour is shown in
Figure 2 depending on irradiation time.
As a control experiment a silver salt(AgNO3) in DMF with and without POSS-NH2 which
used as precursor for the synthesis of POSS-TX were irradiated by UV-Light and formation of
Ag NPs were detected as shown in Figure 3 but the shape of curves and at least 10 nm shifting
of max indicates the agglomeration of Ag NPs and the size differentiation. Light-assisted
methods for preparation of Ag NPs were found in the literature[31-34] and as reported in
earlier works in some cases the solvent itself acted as reducing agent for formation of Ag NPs
- 7 -

even in the absence of light source[35]. The formation of Ag NPs in organic solvents such as
DMF and alcohols[34] by direct excitation were found, as we have also presented in Figure 4.
UV-cured nanocomposite thin films were prepared by photopolymerization experiments and
one-component photoinitiator POSS/TX containing PEGMEA/PEGDA formulation in the
presence and absence of AgNO3 salt was coated on glass substrate and over-cured underneath
a mini-UV-cure unit, with 200 pass times. SEM pictures were taken directly from the surface
of the cured coating and showed us a very interesting wrinkled pattern (see Figure 5) for
formulation consist of Ag NPs.
Photocured formulation with POSS-TX in the absence of the silver salt was displayed
different morphology than Ag NPs containing formulation as given in Figure 6. Indeed,
incorporation of POSS skeletal to the polymer matrix in the absence of Ag NPs was clearly
seen from SEM images (see Figure 4) but certainly morphology was not similar to the
wrinkled pattern which was obtained simultaneously formed and nicely distributed Ag NPs in
photocured polymeric films with POSS-TX.
Controlled size and distribution of well-defined Ag NPs were obtained in the self-wrinkled
coating with the contribution of POSS structure. The sizes of the Ag NPs were nearly uniform
- 8 -

at around 18-23 nm and they were packed closely in self-wrinkled pattern (see Figure 3).
Photocured self-wrinkled surface formation was recently reported by Jiang et al. [36] by using
fluorinated polymer, silver precursor, benzophenone as the Type II photoinitiator, and amine
as the co-initiator. Self-wrinkling patterned surface of photocured coatings prepared by
fluorinated POSS containing thiol groups (F-POSS-SH) as the nanoadditive and additionally
used for overcoming the oxygen inhibition [37, 38].
One may think that since TX is a Type II photoinitiator, that TX-attached POSS will not
work for the polymerization of monomers without a coinitiator and as a result that it will not
covalently link to the polymer matrix. But this is not the case for our POSS-TX initiator
because the amino functionality of one–component POSS-TX is responsible as a source of
hydrogen donation. According to unpublished results, the initiating efficiency was determined
for the photopolymerization of methyl methacrylate as model acrylate in air atmosphere and
the obtained polymer confirmed that the POSS-TX structure was attached to the polymer via
intramolecular hydrogen abstraction which led to formation of the ketyl radical. The power of
ketyl radicals for photoreduction of metal salts especially silver salts is already known. Indeed,
this process has been shown by many researchers, and we also recently reported the
photoreduction of HAuCl4 to Au NPs [39-43]. The mechanism of formation of Ag NPs by
using POSS-TX is depicted in the light of previously used mechanistic studies and given in
Scheme 2. The POSS unit in the POSS-TX structure is possibly responsible for formation of
the wrinkled surface since it covalently attached to the polymer backbone.
Another control experiment was performed to see the effect of SPR absorption of Ag NPs on
the photopolymerization. Experiment was conducted with POSS-NH2 and silver salt(AgNO3)
containing PEGMEA/PEGDA formulation without an initiator irradiation by UV light since
there was no initiating species no polymerization was observed.
4. Conclusions
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In conclusion, TX-functionalized Polyhedral Oligomeric Silsesquioxanes (POSS-TX) self-
assemble with Ag NPs into well-defined spherical nanoparticles (18-23 nm), providing
wrinkle-structured nanocomposites.
5. References
[1]
J.P. Fouassier, Photoinitiation, Photopolymerization and Photocuring: Fundamental
and Applications, Hanser Publishers, New York, NY 1995.
[2]
Y. Yagci, S. Jockusch, N.J. Turro, Photoinitiated Polymerization: Advances,
Challenges, and Opportunities, Macromolecules 43 (2010) 6245-6260.
[3]
J.P. Fouassier, J. Lalevee. Photoinitiators for Polymer Synthesis: Scope, Reactivity
and Efficiency, Wiley-VCH, Weinheim, 2012.
[4]
R. Schwalm, UV Coatings-Basics, Recent Developments and New Application, 1st ed.,
Elsevier, Amsterdam, The Netherlands, 2007.
[5]
C. Decker, Kinetic Study and New Applications of UV Radiation Curing, Macromol.
Rapid Commun. 23 (2002) 1067-1093.
[6]
H. Benjamin, D. William, G. Giulia, D. Fazzi, F. Brandi, A. Petrozza, A. Diaspro,
Polymerization Inhibition by Triplet State Absorption for Nanoscale Lithography, Adv. Mater.
25 (2013) 904-909.
[7]
H. Lu, J.W. Stansbury, J. Nie, A.K. Berchtold, C.N. Bowman, Development of highly
reactive mono-(meth)acrylates as reactive diluents for dimethacrylate-based dental resin
systems, Biomaterials 26 (2005) 1329-1336.
[8]
C. Kumar, Metallic Nanomaterials, Wiley, Weinheim, 2009.
[9]
D.S. Esen, G. Temel, D.K. Balta, X. Allonas, N. Arsu, One-component thioxanthone
acetic acid derivative photoinitiator for free radical polymerization, Photochemistry And
Photobiology 90 (2014) 463-469.
[10] F. Karasu, N. Arsu, S. Jockusch, N. J. Turro, Thioxanthone Hydroquinone-O,O '-
diacetic Acid: Photoinitiator or Photostabilizer?, Journal Of Organic Chemistry, 78 (2013)
- 10 -

9161-9165.
[11] F. Karasu, N. Arsu, S. Jockusch, N. Turro, Mechanistic studies of photoinitiated free
radical polymerization using a bifunctional thioxanthone acetic acid derivative as
photoinitiator, Macromolecules, 42 (2009) 7318-7323.
[12] F. Karasu, M. Aydin, M.A. Kaya, D.K. Balta, N. Arsu, Determination of
photoinitiated polymerization of multifunctional acrylates with acetic acid derivatives of
thioxanthone by RT-FTIR, Progress In Organic Coatings 64 (2009) 1-4.
[13] D.K. Balta, N. Arsu, Photodimerization of thioxanthone–anthracene: formation of
monochromophoric Type II initiator, Designed Monomers And Polymers 19 (2016) 222-226.
[14] U. Ay, Z. Dogruyol, N. Arsu, The effect of heavy metals on the anthracene–Me-β-
cyclodextrin host–guest inclusion complexes, Supramolecular Chemistry 26 (2014) 66-70.
[15] D.K. Balta N. Arsu, Thioxanthone-ethyl anthracene, Journal Of Photochemistry And
Photobiology A: Chemistry, 257 (2013) 54-59.
[16] S. Kork, G. Yilmaz, Y. Yagci, Poly (vinyl alcohol)–Thioxanthone as One‐Component
Type II Photoinitiator for Free Radical Polymerization in Organic and Aqueous Media,
Macromol. Rapid Commun. 36 (2015) 923-928.
[17] G. Temel, N. Arsu, Y. Yagci, Polymeric Side Chain Thioxanthone Photoinitiator for
Free Radical Polymerization, Polym. Bull. 57 (2006) 51-56.
[18] B. Gacal, H. Akat, D.K. Balta, N. Arsu, Y. Yagci, Synthesis and characterization of
polymeric thioxanthone photoinitatiors via double click reactions, Macromolecules 41 (2008)
2401-2405.
[19] N. Karaca, D.K. Balta, N. Ocal, N. Arsu, Mechanistic studies of thioxanthone–
carbazole as a one-component type II photoinitiator, J. Lumin., 146 (2014) 424-429.
[20] S.S. Dadashi, C. Aydogan, Y. Yagci, Shining a light on an adaptable photoinitiator:
advances in photopolymerizations initiated by thioxanthones, Polym. Chem. 6 (2015) 6595-
6615.
[21] J. Lalevee, M.A. Tehfe, F. Dumur, D. Gigmes, B. Graff, F. Morlet-Savary, J.
Fouassier, Light-Harvesting Organic Photoinitiators of Polymerization, Macromol. Rapid
- 11 -

Commun. 34 (2013) 239-245.
[22] J. Lalevee, N. Blanchard, M.A. Tehfe, C. Fries, F. Morlet-Savary, D. Gigmes, J.P.
Fouassier, New thioxanthone and xanthone photoinitiators based on silyl radical chemistry,
Polym. Chem. 2 (2011) 1077-1084.
[23] H. Akat, B. Gacal, D.K. Balta, N. Arsu, Y. Yagci, Poly (ethylene glycol)-thioxanthone
prepared by Diels–Alder click chemistry as one-component polymeric photoinitiator for
aqueous free-radical polymerization, J. Polym. Sci., Part A: Polym. Chem. 48 (2010) 2109-
2114.
[24] G. Temel, N. Arsu, One-pot synthesis of water-soluble polymeric photoinitiator via
thioxanthonation and sulfonation process, J. Photochem. Photobiol. 202 (2009) 63–66.
[25] D.K. Balta, G. Temel, M. Aydin, N. Arsu, Thioxanthone based water-soluble
photoinitiators for acrylamide photopolymerization, Eur. Polym. J., 46 (2010) 1374.
[26] S. Dadashi-Silab, C. Aydogana, Y. Yagci, Shining a light on an adaptable
photoinitiator: advances in photopolymerizations initiated by thioxanthones, Polym Chem. 6
(2015) 6595-6615.
[27] J.B. Carroll, B.L. Frankamp, V.M. Rotello, Self-assembly of gold nanoparticles through
tandem hydrogen bonding and polyoligosilsequioxane (POSS)–POSS recognition processes,
Chem. Commun., 17 (2002) 1892-1893.
[28] R.H. Baney, M. Itoh, A. Sakakibara, T. Suzukit, Silsesquioxanes, Chem. Rev. 95
(1995) 1409-1430.
[29] M. Aydin, N. Arsu, Y. Yagci, One-Component Bimolecular Photoinitiating Systems,
2, Macromol. Rapid Commun. 24 (2003) 718–723.
[30] Z.L. Zhou, O. Brandstein, R.D. Stramel, G.A. Lane, WO2016122454 (A1)- Polymeric
Photo Active Agents, PatentPak.
[31] M. Rycenga, C. M. Cobley, J. Zeng, W. Li, C. H. Moran, Q. Zhang, D. Qin, and Y.
Xia., Controlling the Synthesis and Assembly of Silver Nanostructures for Plasmonic
Applications, Chem. Rev. 111(6), (2011), 3669-3712.
- 12 -

[32] M. Sakamoto, M. Fujistuka,T. Majima., J.Photochem and Photobiol. C: Photochemistry
Reviews, 10(2009), 33-56.
[33] K. Stamplecoskie, J. Scaiano., Photochem &Photobiol., 88(4), (2012), 762-768.
[34] N.L. Pacioni, C.D. Borsarelli,V. Rey and A.V.Veglia., “Synthetic Routes for the
Preparation of Silver Nanoparticles A Mechanistic Perspective”., Silver Nanoparticle
Application, Springer Int. Pub.Switzerland, Ed.E.I Alarcon,M.Griffith, K.I.Udekwu, (2015)
pp-13-46
[35] SunY., Controlled synthesis of colloidal silver nanoparticlesin organic solutions: empirical
rules for nucleation engineering., Chem.Soc.Rev., 42, (2013), 2497-2511.
[36] H. Lin, Y. Wang, Y. Gan, H. Hou, J. Yin, X. Jiang, Simultaneous Formation of a
Self-Wrinkled Surface and Silver Nanoparticles on a Functional Photocuring Coating,
Langmuir 31 (2015) 11800–11808.
[37] Y. Gan, X. Jiang, J. Yin, Self-Wrinkling Patterned Surface of Photocuring Coating
Induced by the Fluorinated POSS Containing Thiol Groups (F-POSS-SH) as the Reactive
Nanoadditive, Macromolecules, 45 (2012) 7520-7526.
[38] H. Hou, Y. Gan, J. Yin, X. Jiang, Multifunctional POSS-Based Nano-Photo-Initiator
for Overcoming the Oxygen Inhibition of Photo-Polymerization and for Creating Self-
Wrinkled Patterns, Adv. Mater. Interfaces, 1 (2014) 1400385.
[39] T. Ceper, N. Arsu, Photochemically Prepared Gold/Polymer Nanocoatings: Formation
of Gold Mirror, Macromol. Chem. Phys. 218 (2017) 1700030.
[40] L. Balan, V. Melinte, T. Buruiana., R. Schneider, L. Vidal, Controlling the
morphology of gold nanoparticles synthesized photochemically in a polymer matrix through
photonic parameters, Nanotechnology 23 (2012) 415705.
[41] M.L. Marin, K.L. McGilvray, J.C. Scaiano, Photochemical strategies for the synthesis
of gold nanoparticles from Au(III) and Au(I) using photoinduced free radical generation, J.
Am. Chem. Soc., 130 (2008) 16572-16584.
- 13 -

[42] Y. Yagci, M. Sangermano, G. Rizza, In situ synthesis of gold-cross-linked
poly(ethylene glycol) nanocomposites by photoinduced electron transfer and free radical
polymerization processes, Chem. Commun., 24 (2008) 2771-2773.
[43] B. Zhang, Q. Zhang, H. Zhang, X. Lei, D. Yin, X. Fan, L. Zhou, Preparation of
diamine-POSS/Ag hybrid microspheres and its application in epoxy resin, Journal of Polymer
Research, 19 (2012) 9986.
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Scheme 1. Synthesis of POSS-TX
Scheme 2. In-situ photoinduced formation mechanism of Ag NPs with POSS-TX for
PEGMEA/PEGDA monomer system
- 15 -

Figure 1. Absorption spectrum of Ag NPs obtained from photoreduction of AgNO3 (40 mg,
4%wt) with TXOCH2CONH(CH2)3POSS (5 mg, 0.5%wt) in DMF depending on irradiation
time by UV-Vis spectroscopy
Figure 2. The colour change of irradiated solution of TXOCH2CONH(CH2)3POSS and
AgNO3 in DMF
- 16 -

Figure 3. Absorption spectrum of Ag NPs obtained from photoreduction of AgNO3 (40 mg,
4%wt) with POSS-NH2 (5 mg, 0.5%wt) in DMF depending on irradiation time by UV-Vis
spectroscopy
- 17 -

Figure 4. Absorption spectrum of Ag NPs obtained from photoreduction of AgNO3 (40 mg,
4%wt) in DMF depending on irradiation time by UV-Vis spectroscopy
- 18 -

Figure 5. SEM images of UV-cured coatings consisting of POSS-TX (5 mg, 0.5%wt) /
AgNO3 (40 mg, 4%wt) in PEGMEA/PEGDA
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Figure 6. SEM images of UV-cured coatings consisting of POSS-TX (5 mg, 0.5%wt) in
PEGMEA/PEGDA
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