Accelerat ing t he world's research.

Micro continuous flow-through

synthesis of triangular silver
nanoprisms and their incorporation
in complexly com...
Wolfgang Fritzsche

Chemical Engineering Journal

Cite this paper Downloaded from Academia.edu 

Get the citation in MLA, APA, or Chicago styles

Related papers Download a PDF Pack of t he best relat ed papers 

Nanopart icle synt hesis in microreact ors

Lizhong He

Microfluidics for part icle synt hesis from phot ocrosslinkable mat erials
David Baah, Tamara Floyd-smit h

Porous Polymer Part icles - A Comprehensive Guide t o Synt hesis, Charact erizat ion, Funct ionalizat ion …
M. Talha Gokmen
 Chemical Engineering Journal 227 (2013) 191–197

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Micro continuous flow-through synthesis of triangular silver nanoprisms

and their incorporation in complexly composed polymer microparticles
Andrea Knauer a,⇑, Andrea Csáki b, Wolfgang Fritzsche b, Christophe A. Serra c, Nicolas Leclerc c,
J. Michael Köhler a
a
Ilmenau University of Technology, Institute for Physics, Dept. of Physical Chemistry and Micro Reaction Technology, Weimarer Str. 32, D-98693 Ilmenau, Thuringia, Germany
b
Institute for Photonic Technologies, Dept. of NanoBiophotonics, Albert-Einstein-Str. 9, 07745 Jena, Germany
c
Université de Strasbourg (UdS), Ecole de Chimie Polymères et Matériaux (ECPM), Laboratoire d’Ingénierie des Polymères pour les Hautes Technologies (LIPHT), EAc(CNRS) 4379,
Groupe d’Intensification et d’Intrapolation des Procédés Polymères (G2IP), 25 rue Becquerel, Strasbourg Cedex 2, F-67087, France

h i g h l i g h t s

" Segmented flow-through synthesis of very homogeneous triangular Ag nanoprisms.

" High yield and highly homogeneous silver nanoprisms due to mixing enhancement through segment internal convection.
" Incorporated Ag nanoprisms in polymer matrix and formation of hydrogel-polymer composite particles.
" Processing of Janus-like particles with a hydrophilic nanoparticle-containing composite part as possible sensor beads.

a r t i c l e i n f o a b s t r a c t

Article history: The micro fluid segment technique is used for the continuous-flow synthesis for small silver nanoparti-
Available online 17 July 2012 cles by reduction of silver ions with sodium borohydride in aqueous solution and for the growth of tri-
angular silver nanoprisms. In result, triangular nanoprisms are obtained in very high yield and high
Keywords: homogeneity. The tuning of the in-plane dipole plasmon resonance can easily be controlled by choosing
Ag nanoprisms suited flow rate ratios of silver salt solution and colloidal solution of seed nanoparticles or by different
Plasmonic nanoparticles silver salt concentrations. The colloidal aqueous solutions of metal nanoparticles can be used for the
Micro segmented flow
preparation of mixtures with water-soluble monomers as acrylamide and for the formation of hydro-
Composite polymer particles
Janus particles
gel-polymer composite particles in a droplet-based photopolymerization process. Beside spherical com-
Co-flow synthesis posite particles, Janus particles with a hydrophilic nanoparticle-containing composite part are prepared
Micro fluidics by a combined photopolymerization of the aqueous acrylamide reaction mixture together with embed-
ded droplets of an acrylate-based monomer (Tripropylene Glycol Diacrylate, TPGDA) mixture in a micro
co-flow twin arrangement. The components of the mushroom-like particles can easily be distinguished
by optical microscopy due to their light-scattering and fluorescence behavior.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction chemical catalysis and analytical procedures to bio screening and

Shape anisotropic nanoparticles of gold and silver are of great
interest due to their size- and geometry-dependent plasmonic
absorption in the long wavelength range [1,2]. The color of triangle
silver nanoprisms can be tuned by the lateral length of these crys-
tals [3–6]. Composite particles unify the properties of different
materials [7]. A well-defined composition, size, shape and morphol-
ogy of such composed particles is demanded for applications in a
large spectrum reaching from micro and nanotechnology over
⇑ Corresponding author. Address: University of Technology Ilmenau, Germany,
Institute for Chemistry and Biotechnology, Weimarer Str. 32, D-98693 Ilmenau,
Germany. Tel.: +49 0 3677 693689; fax: +49 0 3677 693173.
E-mail address: Andrea.Knauer@TU-Ilmenau.de (A. Knauer).
drug development [8–12]. Microfluidic steps in the synthesis of
simple and hierarchically structured particles have been introduced
in order to achieve a very high reproducibility in the formation of
the single particles and the possibility of tuning the particle proper-
ties. Microfluidic procedures have been proved to be particularly
suited for the generation of polymer core/shell particles [13–15],
for composed microparticles with tunable sizes [13,16–19] and
so-called Janus particles [20–23] and for the incorporation of inor-
ganic nanoparticles in polymer microparticles [24–28]. Microfluidi-
cally generated hierarchically composed particles incorporating
metal nanoparticles can be of great interest for heterogeneous
catalysis [29–31].
Nanoporous microparticles incorporating chemically active
nanoparticles are of particular interest, because they unite the

1385-8947/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.07.041
192 A. Knauer et al. / Chemical Engineering Journal 227 (2013) 191–197
handling advantages of the microparticles, for example in separa-
tion steps, washing and for solid state chemistry, and the advanta-
ges of a large ensemble of nanoparticles including the extremely
high surface-to-volume ratio. Beside this integration of nanoparti-
cles, a labeling of microparticles is required if an individual particle
should be recognized or processed in a specific process chain. The
combination of functional properties based on the integrated
nanoparticles and the matrix nanoporosity with a labeling of the
microparticle is of interest in single particle operations.
The application of a ternary system of immiscible liquids allows
realizing composed particles in a droplet-based microfluidic proce-
dure. This technique can be applied in order to generate amphi-
philic microparticles. Here, the microfluidic generation of
composed polymer microparticles consisting of a part with a label-
ing function and a functional part with a nanoporous matrix incor-
porating metal nanoparticles is reported.
In case of wet chemically processed Ag nanoparticles it is ex-
pected, that the homogeneity of nucleation and particle growth
is influenced by the mixing speed due to the strong effect of reac-
tant concentrations on the nucleation rate. In addition, the reaction
of PSSS (poly(sodium styrenesulphonate)) with the first reducing
agent and the following interaction between the reduced sulfonic
groups and the Ag seeds will also affect the homogeneity of the
product particles. Therefore, their quality should improve, if high
mixing rates under micro continuous-flow conditions and narrow
residence time distributions are applied [32]. This work demon-
strates the potential of the micro reaction technique for the gener-
ation of multiscale Janus microparticles. Triangular silver
nanoprisms were chosen as an advanced, plasmonic material with
exact tunable optical properties. A dispersion of these shape aniso-
tropic noble metal nanoparticles in an aqueous acrylamide matrix
serves as carrier liquid in which droplets of a TPGDA/fluorescence
dye mixture are formed. In a second process of droplet formation,
this emulsion is dosed into a PDMS carrier stream and TPGDA/
acrylamide double droplets emerge. By irradiation with UV light,
the polymerization process is initiated. Thus, multiscale functional
Janus microparticles are obtained, which are of great interest for a
further investigation of their sensory potential.
2. Experimental
2.1. Microfluidic arrangements for the continuous-flow synthesis of
silver seeds and nanoprisms
The protocols for the synthesis of silver seeds and silver nanop-
risms are an adapted version of the batch synthesis protocol of
Aherne et al. [32,33]. The micro segmented flow-through tech-
nique was chosen for the formation of silver seed nanoparticles
as well as for the growth of noble metal nanoparticles during the
formation of the non-spherical Ag nanoprisms. A double injector
unit (Fig. 1a) was applied for the injection of an aqueous sodium
citrate solution (2.5 mmol/L) and a mixture of sodium polystyrene
sulfonate (500 mg/L) and a solution of sodium borohydride
(2.5 mmol/L) into a continuous flow of the carrier liquid (Perflu-
oro(methyldecalin)). At a second injection unit, silver nitrate solu-
tion (2.5 mmol/L) was dosed into the preformed fluid segments. In
result, fluid segments of the reaction mixture of regular size and
distance are formed. The constant flow conditions of all compo-
nents ensure constant conditions for transport of all components
and constant mixing and reaction conditions.
PC-controlled syringe pumps (Cetoni NeMESYS, Cetoni GmbH,
Korbußen, Germany) and syringes with glass tubes are used in or-
der to realize well-controlled fluid actuation and a fluid transport
with suppressed pulsations. The quality of the generated fluid seg-
ments was controlled by micro flow-through photometers oper-
ated with a measurement frequency of 10 kHz.
A total flow rate of 600 lL/min has been applied for the actua-
tion of the silver salt solution, sodium citrate solution, PSSS and the
reducing agent. The flow rate of the carrier solution was 1000 lL/
min resulting in a total flow rate of 1600 lL/min and a transport
velocity of segments of 136 mm/s. The PTFE ware for segment gen-
eration and the PTFE and FEP reactor tubing (Bohlender GmbH,
Gruensfeld, Germany) have an inner diameter of 0.5 mm. This
diameter corresponds with a typical volume of the formed seg-
ments between 100 and 200 lL at a length in the range of 0.5
and 1 mm.
After a residence loop of a length of 1000 mm, the product solu-
tion of seed nanoparticles was collected in a tube and separated
from the carrier phase.
The seed solution was diluted to 10% of the original seed con-
centration and mixed with a reducing agent solution (ascorbic acid
in water: 20 mmol/L). This solution was used for the continuous-
flow synthesis of the silver prisms in a second microfluidic process
using the micro segmented flow-through technique (Fig. 1b) by
forming segments with in situ mixing of the seed solution and an
aqueous silver nitrate solution (1 mmol/L).
2.2. Microfluidic arrangement for the synthesis of metal/polymer
composite particles
The microfluidic arrangement for the preparation of complexly
composed polymer microparticles with incorporated silver nano-
particles was based on the co-flow arrangement for the generation
of double droplets followed by downstream in situ photopolymer-
ization [34,35]. The arrangement consists of two capillary-based
droplet generators in a row (Fig. 2). The first one, composed of a
simple 1/16’’ T-junction (P-728-01, Upchurch Scientific) and a glass
capillary of roughly 500 lm ID, allows for the production of drop-
lets of an organic solution consisting in a acrylate-based monomer
(TPGDA), an organic fluorescent dye (4-octyl-7-(5-octyl-thiophen-
2-yl)-benzol[1,2,5]thiadiazole) and a photoiniatiator (1-hydrox-
ycyclohexyl phenyl ketone, HCPK) in a continuous stream of an
aqueous solution composed of distilled water, acrylamide (AA), a
crosslinker (NN0 -methylene-bisacrylamide), a photoiniatiator
(GENOCURE DMHA) and silver nanoparticles. The second droplet
generator, composed of another T-junction and a smaller capillary,
allows to emulsify the previous aqueous solution into droplets in a
carrier stream of polydimethylsiloxane (PDMS, 500 cSt.).
2.3. Chemicals and materials
All applied chemicals are pA grade. The following chemicals
have been used as received: Silver nitrate (Merck KGaA, Darmstadt,
Germany, purity: 99%), sodium borohydride (Merck KGaA, Darms-
tadt, Germany, purity: 99%), and poly(sodium styrenesulphonate)
(PSSS) (ACROS Organics, Morris Plains, USA/NJ, MW 70.000) were
used for the synthesis of the Ag seed nanoparticles. Ascorbic acid
(Merck KGaA, Darmstadt, Germany, purity: 99.7%) served as the
reducing agent for the subsequent prism growth. Sodium citrate
(Merck KGaA, Darmstadt, Germany, purity: 99%) is necessary for
the stabilization of the obtained triangular Ag nanoprisms.
Tri(propylene glycol) diacrylate (TPGDA), 1-hydroxycyclohexyl
phenyl ketone (HCPK), acrylamide (AA), polydimethylsiloxane
(PDMS) were purchased from Aldrich (France) and used as re-
ceived. NN0 -methylene-bisacrylamide and GENOCURE DMHA were
purchased respectively form Acros (Fance) and Rahn USA Corp.
(USA) and also used as received.
2.4. Characterization
Differential centrifugal sedimentation spectroscopy (DCS, DC
20000, CPS Instruments Inc., Newtown, USA/PA) was used for the
 A. Knauer et al. / Chemical Engineering Journal 227 (2013) 191–197 193

Fig. 1. Microfluidic arrangements for the preparation of triangular silver nanoprisms by micro continuous-flow processes using the fluid segment technique with
perfluoromethyldecalin as carrier medium: (a) generation of silver seeds by mixing an aqueous solution of sodium borohydride containing the polyanionic polymer PSSS with
a silver nitrate solution in the presence of sodium citrate, (b) growth of shape anisotropic nanoparticles from the preformed silver seed nanoparticles by mixing the colloidal
solution of silver seed particles with ascorbic acid and further silver nitrate solution.

Fig. 2. Experimental arrangement for the preparation of complexly composed polymer particles by combined photopolymerization of acrylamide and TPGDA under co-flow
in a three-step process (from left to right): (1) forming of droplets of TPGDA reaction mixture inside a stream of an aqueous solution of acrylamide containing a crosslinker
and the Ag nanoprisms using a glass capillary inside a second glass tube, (2) forming of composed droplets of the TPGDA- and the acrylamide-monomer-mixture using a
second glass capillary inside a second glass tube, (3) transport of the formed TPGDA/acrylamide double-droplets through a FEP tube (inner diameter 0.5 mm) and initiation of
polymerization by UV radiation.

determination of the size distribution spectra of silver seed nano-
particles and the stokes equivalent sedimentation diameter distri-
bution of the triangular silver nanoprisms. The SEM images have
been obtained by means of two JEOL instruments (JSM 6380 and
JSM 6700 F, JEOL, Tokyo, Japan). A fluorescence microscope (Axio-
Plan, Carl Zeiss AG, Jena, Germany) was used for the optical images.
3. Results and discussion
3.1. Synthesis of silver seeds
Well-controlled fluidic conditions for the formation of regular
particles with homogeneous distributions of size, shape, and com-
position are required for (i) the formation of the Ag seed nanopar-
ticles, (ii) during the initiation of the anisotropic growth of silver
prisms in the second process step, (iii) for the formation of the pro-
portionally larger polymer particles. A fast mixing and constant
conditions of transport during the interval of silver nucleation have
been achieved by a micro segmented flow-through synthesis of the
silver seeds. High flow rates induce under these conditions an
intensive segment-internal convection and mixing between the
reducing agent (sodium borohydride) and the metal salt solution,
which leads to a very fast initiation of the nucleation process and
therefore to a narrow time interval for the nucleation process.
The formation of shape anisotropic particles is obviously caused
by a partial reduction of the sulfonic groups of PSSS by sodium
194 A. Knauer et al. / Chemical Engineering Journal 227 (2013) 191–197

borohydride. An interplay between silver ions and water-soluble

polymer, applied in a low concentration, determines the nucleation
rate and the initial growth behavior, as well as the attachment of
polymer molecules on the arising nanoparticles (Fig. 3).
In the first step of the Ag seed nucleation, the mixing of NaBH4
and PSSS was initiated. In the second step, silver ions were added.
The comparatively high total flow rate (1.6 mL/min) in relation to
low volumes of micro fluidic segments (about 400 lL) ensure that
the time needed for mixing is low compared to the rate of the
chemical reaction. This leads to a formation of highly homoge-
neous Ag seed particles.

3.2. Synthesis of silver nanoprisms

In a second synthesis procedure, silver ions and a reducing

agent are dosed into microfluidic droplets containing Ag seed
nanoparticles in order to form silver nanoprisms that display high
homogeneity in size distribution. The homogeneity of fluid trans-
port and mixing conditions ensure a homogeneous start of the fur-
ther particle growth. As known from the batch experiments, the
silver particles show a comparatively fast growth in one plane
but only a delayed growth in the third direction, under the chosen
conditions. The growth is controlled by the crystallographic planes.
This growth behavior results in to the formation of a triangular
(or disk-like) prismaticshape (Fig. 4).
The presented technique can be adapted to synthesize colloidal
solutions with tuneable particle sizes. Thus, the long-wavelength
absorption can be shifted in situ in a range between 550 and
900 nm. The edge length is determined by the ratio of seed nano-
particles introduced to the growth process and the concentration
of available silver ions for reductive metal deposition. The regular-
ity in the obtained wave lengths corresponding to the electronic in-
plane oscillation as well as the shift in the absolute absorbance of
colloidal product solutions prove the high homogeneity and repro-
ducibility of the synthesis under different flow rate ratios of the
reactants (Fig. 5a and b).
3.3. Incorporation of silver nanoprisms in polyacrylamide hydrogel
microparticles and in Janus polymer particles
The incorporation of prismatic silver particles inside poly(acryl-
amide) hydrogel microparticles succeeded by photoinitiated
Fig. 4. Example of silver nanoprisms prepared by the two-step segmented flow
process.
polymerization of droplets of an aqueous solution of a monomer
mixture, a crosslinker, a photoinitiator, and the silver nanoprisms
in a colloidal disperse distribution. Thus, a homogeneous distribu-
tion of silver nanoprisms inside the forming hydrogel particle is
achieved. It is assumed that the position of each silver nanoprism
becomes fixed during the formation of the polymer crosslinked
network after the photochemical initiation of the polymerization.
The reaction mixture and later the hydrogel of the microparticles
remained dyed due to the plasmonic absorption of the silver
nanoprisms inside the polymer matrix.
The process steps for the formation of complex composite par-
ticles are illustrated in Fig. 6. Primarily, an acrylamide solution
containing the Ag nanoprisms was prepared. Thereafter, the more
lipophilic monomer TPGDA was admixed with a photoinitiator and
a matrix-compatible fluorescent dye. Then, both photosensitive
mixtures were fed together as it is shown in Fig. 2 in order to form
complexly composed polymer particles.
In a first experiment, spherical microparticles prepared from
the above two photosensitive mixtures were prepared separately.
Both particle types can easily be distinguished by their optical
properties. A dark-field image as well as a fluorescence image of
the same area with a mixture of poly(TPGDA) microparticles,
poly(acrylamide) microparticles (after drying) and a second group

Fig. 3. Hypothetical mechanism for the formation of triangular silver nanoprisms: more or less cubic or spherical metal nanoparticles are formed if no symmetry breaking
occurs (left), the chemisorption of one polyelectrolyte molecule – probably with a certain number of thiol-groups formed by reduction of some of the original sulfonic acid
groups – leads to a symmetry breaking resulting in a polarization (nano-local electrostatic pressure) directed to the periphery of the silver nanoparticle and supporting an
anisotropic deposition of further silver leading to a growth of flat, triangular prisms.
 A. Knauer et al. / Chemical Engineering Journal 227 (2013) 191–197
Fig. 5. (a) Optical absorption spectra of triangular silver nanoprisms obtained by
micro segmented flow-through synthesis in the presence of various seed nanopar-
ticle volumes. (b) Corresponding DCS analysis data. The DCS spectra show the
Stokes equivalent sedimentation radius of the flat, laterally extended Ag
nanoprisms.
Fig. 6. Schematic illustration of the synthesis strategy for complexly composed polymer microparticles incorporating prismatic silver nanoprisms.
195
of smaller poly(TPGDA) particles without dye are shown in Fig. 7.
The poly(TPGDA) microparticles have an amorphous structure
and a smooth surface. This results into a lower scattering of light
and a glass-like appearance (Fig. 7a). In contrast, the poly(acrylam-
ide) microparticles have a porous structure and display an effective
light scattering, which leads to a white (bright) appearance in the
dark field illumination. The contrast conditions were inverted by
switching from dark field to fluorescence imaging (Fig. 7b). Now,
the fluorescence-dye containing poly(TPGDA) microparticles are
shining brightly, but the poly(acrylamide) microparticles appear
dark.
Composed Janus microparticles consisting of two different parts
were obtained in experiments with both the acrylamide/silver
nanoparticles mixture and the TPGDA/dye mixture using the co-
flow arrangement (Fig. 2). These Janus particles are composed of
a cylinder-like part of poly(acrylamide) and a head-like part of
dyed poly(TPGDA) resulting in a mushroom-like shape morphol-
ogy. The different parts of the polymer matrix can easily be identi-
fied by a comparison of the dark-field and the fluorescence
microscope images (Fig. 8). The interaction of both polymer matri-
ces of composed microparticles is in complete coincidence with the
character of the separately synthesized spherical particles: The
poly(TPGDA) head groups appear dark and glassy in the dark-field
image, but bright under UV illumination, while the poly(acrylam-
ide) cylinder groups appear bright due to effective light scattering
in the dark-field mode and dark under UV-irradiation. Only in the
direct environment of the head material, a scattering of the fluores-
cence light emanated by the poly(TPGDA) matrix causes a certain
brightening of the close poly(acrylamide) matrix.
4. Conclusions
Triangular silver nanoprisms can be prepared in very high qual-
ity and high yield of the desired shape by application of the micro
segmented flow technique for the synthesis of the silver seed
nanoparticles as well as for the process step of the nanoprism
growth. The optical properties of the plasmonic silver nanoprisms
can be tuned by the flow rate ratios of the colloidal solution of
silver seed particles and the flow rate or the concentration of the
silver nitrate solution for the particle growth. The obtained
196 A. Knauer et al. / Chemical Engineering Journal 227 (2013) 191–197

Fig. 7. Dark-field microscopic image (left) and fluorescence microscopic image (right) of a mixture of three different spherically shaped polymer microparticles prepared
separately by a droplet-based photopolymerization process [19]: dye-doped poly(TPGDA) microparticles (bright appearance in the fluorescence image), smaller dye-free
poly(TPGDA) microparticles (dark in both images), light-scattering silver-nanoparticles containing cross-linked poly(acrylamide) microparticles (bright appearance in the
dark-field image).

Fig. 8. Dark-field microscopic image (left) and fluorescence microscopic image (right) of Janus polymer composite microparticles consisting of a fluorescent part of a
poly(TPGDA)-matrix (mushroom heads) and a light scattering cylindrical part of a dried crosslinked poly(acrylamide) matrix containing silver nanoprisms.

colloidal solutions can be used for the preparation of aqueous solu-
tions of acrylamide and for an introduction of these mixtures into a
droplet-based photopolymerization process for the generation of
inorganic nanoparticles-loaded polymer microparticles.
This technique can also be applied for the generation of Janus
microparticles with a fluorescent lipophilic part if the micro con-
tinuous-flow photopolymerization of droplets of a nanoparticle-
containing acrylamide mixture is combined with droplet formation
of a photopolymerizable mixture of TPGDA in a co-flow
arrangement.
The route for preparation of complexly composed polymer par-
ticles, which is reported in this work, can be transferred to other
combinations of functional molecules and nanoparticles. It is as-
sumed that similar concepts are suited for the realization of hierar-
chically structured composite particles of different functions by
using the advantages and the flexibility of droplet-based microflu-
idic particles preparation. In particular, the application of synchro-
nous photopolymerization processes for different matrix materials
inside systems of structured fluids will be a promising strategy for
the realization of polymer-based particle architectures incorporat-
ing nanomaterials by application of droplet-based microfluidics.
Acknowledgements
The authors gratefully acknowledge the funding from the DFG
(KO 1403/22-1). In particular the authors thank Steffen Schneider,
Frances Möller (Technical University of Ilmenau), and Ikram-Ullah
Khan (University of Strasbourg) for the technical support. The grat-
itude of the authors is further directed to Alexander Groß and Mike
Günther for the helpful discussions.
 A. Knauer et al. / Chemical Engineering Journal 227 (2013) 191–197
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cej.2012.07.041.
References
[1] K.P. Charle, F. Frank, W. Schulze, The optical-properties of silver
microcrystallites in dependence on size and the influence of the matrix
environment, Ber. Bunsen. Phys. Chem. 88 (1984) 350–354.
[2] E.A. Bondar, Size dependence of optical-properties of small silver particles in
the high-frequency spectral range, Opt. Spektrosk+. 77 (1994) 414–420.
[3] X.Y. Dong, X.H. Ji, J. Jing, M.Y. Li, J. Li, W.S. Yang, Synthesis of triangular silver
nanoprisms by stepwise reduction of sodium borohydride and trisodium
citrate, J. Phys. Chem. C 114 (2010) 2070–2074.
[4] Y. Chen, C.G. Wang, Z.F. Ma, Z.M. Su, Controllable colours and shapes of silver
nanostructures based on pH: application to surface-enhanced Raman
scattering, Nanotechnology 18 (2007).
[5] A.J. Frank, N. Cathcart, K.E. Maly, V. Kitaev, Synthesis of silver nanoprisms with
variable size and investigation of their optical properties: a first-year
undergraduate experiment exploring plasmonic nanoparticles, J. Chem. Educ.
87 (2010) 1098–1101.
[6] A.K. Singh, D. Senapati, A. Neely, G. Kolawole, C.J. Hawker, P.C. Ray, Nonlinear
optical properties of triangular silver nanomaterials, Chem. Phys. Lett. 481
(2009) 94–98.
[7] J.M. Kohler, L. Abahmane, J. Wagner, J. Albert, G. Mayer, Preparation of metal
nanoparticles with varied composition for catalytical applications in
microreactors, Chem. Eng. Sci. 63 (2008) 5048–5055.
[8] J. Reichert, A. Csaki, J.M. Kohler, W. Fritzsche, Chip-based optical detection of
DNA hybridization by means of nanobead labeling, Anal. Chem. 72 (2000)
6025–6029.
[9] N.R. Agarwal, E. Fazio, F. Neri, S. Trusso, C. Castiglioni, A. Lucotti, N. Santo, P.M.
Ossi, Ag and Au nanoparticles for SERS substrates produced by pulsed laser
ablation, Cryst. Res. Technol. 46 (2011) 836–840.
[10] M. Homberger, U. Simon, On the application potential of gold nanoparticles in
nanoelectronics and biomedicine, Philos. Trans. R. Soc. A 368 (2010) 1405–
1453.
[11] K. Liszewski, Applying nanoparticles as molecular tags––Fundamental shift in
biological labeling, Genet. Eng. News 21 (2001) 10+.
[12] M. Muniz-Miranda, SERS-active Ag/SiO2 colloids: photoreduction mechanism
of the silver ions and catalytic activity of the colloidal nanoparticles, J. Raman
Spectrosc. 35 (2004) 839–842.
[13] Z.Q. Chang, C.A. Serra, M. Bouquey, L. Prat, G. Hadziioannou, Co-axial
capillaries microfluidic device for synthesizing size- and morphology-
controlled polymer core–polymer shell particles, Lab Chip 9 (2009) 3007–
3011.
[14] S. Xu, Z. Nie, M. Seo, P. Lewis, E. Kumacheva, H.A. Stone, P. Garstecki, D.B.
Weibel, I. Gitlin, G.M. Whitesides, Generation of monodisperse particles by
using microfluidics: control over size, shape, and composition pg 724, Angew.
Chem. Int. Edit. 44 (2005) 3724–3799.
[15] A.S. Utada, E. Lorenceau, D.R. Link, P.D. Kaplan, H.A. Stone, D.A. Weitz,
Monodisperse double emulsions generated from a microcapillary device,
Science 308 (2005) 537–541.
[16] J. Il Park, A. Saffari, S. Kumar, A. Guenther, E. Kumacheva, Microfluidic
synthesis of polymer and inorganic particulate materials, in: D.R.R.M.Z.F.
Clarke (Ed.), Annu. Rev. Mater. Res. 40 (2010) 415–443.
197
[17] T. Nisisako, T. Torii, T. Higuchi, Novel microreactors for functional polymer
beads, Chem. Eng. J. 101 (2004) 23–29.
[18] C.A. Serra, Z.Q. Chang, Microfluidic-assisted synthesis of polymer particles,
Chem. Eng. Technol. 31 (2008) 1099–1115.
[19] C. Serra, N. Berton, M. Bouquey, L. Prat, G. Hadziioannou, A predictive approach
of the influence of the operating parameters on the size of polymer particles
synthesized in a simplified microfluidic system, Langmuir 23 (2007) 7745–
7750.
[20] Y. Wang, B.H. Guo, X. Wan, J. Xu, X. Wang, Y.P. Zhang, Janus-like polymer
particles prepared via internal phase separation from emulsified polymer/oil
droplets, Polymer 50 (2009) 3361–3369.
[21] R.F. Shepherd, J.C. Conrad, S.K. Rhodes, D.R. Link, M. Marquez, D.A. Weitz, J.A.
Lewis, Microfluidic assembly of homogeneous and janus colloid-filled
hydrogel granules, Langmuir 22 (2006) 8618–8622.
[22] S. Okushima, T. Nisisako, T. Torii, T. Higuchi, Controlled production of
monodisperse double emulsions by two-step droplet breakup in microfluidic
devices, Langmuir 20 (2004) 9905–9908.
[23] H. Zhang, E. Tumarkin, R. Peerani, Z. Nie, R.M.A. Sullan, G.C. Walker, E.
Kumacheva, Microfluidic production of biopolymer microcapsules with
controlled morphology, J. Am. Chem. Soc. 128 (2006) 12205–12210.
[24] K.Y. Van Berkel, C.J. Hawker, PMSE 2-synthesis of composite polymer–metal
nanoparticles by miniemulsion polymerization, Abstr. Pap. Am. Chem S 235
(2008).
[25] K. Mallick, M.J. Witcomb, A. Dinsmore, M.S. Scurrell, Fabrication of a metal
nanoparticles and polymer nanofibers composite material by an in situ
chemical synthetic route, Langmuir 21 (2005) 7964–7967.
[26] D. Zhou, L.P. Yang, R.M. Yang, W.H. Song, S.H. Peng, Y.M. Wang, Functionalized
gold nanoparticles as additive to form polymer/metal composite matrix for
improved DNA sequencing by capillary electrophoresis, Talanta 80 (2009)
195–201.
[27] Z.Q. Chang, C.A. Serra, M. Bouquey, I. Kraus, S.N. Li, J.M. Kohler, Multiscale
materials from microcontinuous-flow synthesis: ZnO and Au nanoparticle-
filled uniform and homogeneous polymer microbeads, Nanotechnology 21
(2010).
[28] J.W. Kim, A.S. Utada, A. Fernandez-Nieves, Z.B. Hu, D.A. Weitz, Fabrication of
monodisperse gel shells and functional microgels in microfluidic devices,
Angew. Chem. Int. Edit. 46 (2007) 1819–1822.
[29] M. Graeser, E. Pippel, A. Greiner, J.H. Wendorff, Polymer core–shell fibers with
metal nanoparticles as nanoreactor for catalysis, Macromolecules 40 (2007)
6032–6039.
[30] V.S.Y. Lin, Gatekeeping effect: surface-functionalized mesoporous metal oxide
and polymer nanoparticles for selective catalysis, Abstr. Pap. Am. Chem S 239
(2010).
[31] J. Keybl, K.F. Jensen, Microreactor system for high-pressure continuous flow
homogeneous catalysis measurements, Ind. Eng. Chem. Res. 50 (2011) 11013–
11022.
[32] A. Knauer, A. Csaki, F. Moller, C. Huhn, W. Fritzsche, J.M. Kohler,
Microsegmented flow-through synthesis of silver nanoprisms with exact
tunable optical properties, J. Phys. Chem. C 116 (2012) 9251–9258.
[33] D. Aherne, D.M. Ledwith, M. Gara, J.M. Kelly, Optical properties and growth
aspects of silver nanoprisms produced by a highly reproducible and rapid
synthesis at room temperature, Adv. Funct. Mater. 18 (2008) 2005–2016.
[34] X. Fernandez-Francos, J.M. Salla, A. Cadenato, J.M. Morancho, A. Mantecon, A.
Serra, X. Ramis, Influence of the initiating mechanism on the cationic
photopolymerization of a cycloaliphatic epoxy resin with arylsulfonium
salts, J. Polym. Sci. Pol. Chem. 45 (2007) 16–25.
[35] P. Panizza, W. Engl, C. Hany, R. Backov, Controlled production of hierarchically
organized large emulsions and particles using assemblies on line of co-axial
flow devices, Colloid Surface A 312 (2008) 24–31.