Synthesis and Characterization of Charged Polystyrene-Acrylic Acid
Latex Particles
P. S. Mohanty,
†
R. Kesavamoorthy,
‡
Kozo Matsumoto,
†
Hideki Matsuoka,*
,†
and
K. A. Venkatesan
§
Department of Polymer Chemistry, Kyoto UniVersity, Kyoto 615-8510, Japan, Materials Science DiVision,
Indira Gandhi Centre for Atomic Research, Kalpakkam-603102, India, and Fuel Chemistry DiVision,
Indira Gandhi Centre for Atomic Research, Kalpakkam-603102, India
ReceiVed NoVember 7, 2005. In Final Form: February 18, 2006
Novel, monodisperse charged colloidal particles of polystyrene cross linked with divinylbenzene and surface-
grafted with acrylic acid were synthesized by emulsion polymerization and were characterized by estimating the
dissociable surface charge by conductivity titration, the particle effective charge by conductivity verses particle
concentration, and the particle size by dynamic light scattering and atomic force microscopy. The structural ordering
and dynamics were investigated as a function of the volume fraction of the particles using static and dynamic light
scattering, respectively. Furthermore, from the electrophoresis measurements, these particles are found to have a high
salt tolerance due to increases in charge as a function of salt concentration.
Introduction
The most fascinating aspect of charged colloidal suspensions
is the appearance of long-range order.
1-3
These structures,
commonly known as colloidal crystals, exhibit iridescence arising
from the Bragg diffraction of visible light.
1
These colloidal crystals
are very important because of their use as Bragg-diffraction
devices
3
, nanoswitches,
4,5
chemical sensors,
6
and templates for
preparing photonic band gap materials.
7,8
Recently, these colloidal
crystalline arrays (CCAs) have been immobilized into an
expandable transparent hydrogel to obtain a gel-sensing device.
7-11
Apart from crystalline order,
1,12
these colloidal suspensions also
exhibit gas,
12-14
liquid,
12,14,15
and even glasslike
12,16,17
order.
The structural ordering and phase transitions in charged colloidal
suspensions can be easily tailored by tuning the range and strength
of the interparticle interaction energy U.
12
This interaction energy
U can be varied over a wide range by changing the Debye
screening parameter κ, which can be achieved by changing the
particle concentration n
p
, the charge on the particle Z, or the salt
concentration C
s
.
Most of the past studies on structural ordering, dynamics, and
phase transitions have been investigated on charged polystyrene
particles having a strong acid group such as sulfonate. Because
of the complete dissociation of the sulfonic groups, these particles
in general carry more charges than particles having weak acid
group. Hence, they can be ordered at lower volume fraction
1
compared to the latter one. However, in the case of a strong acid
group, the particles are not sensitive to pH, and pH control is
very important for a drug delivery system. In the case of a weak
acid group, the particles will have high charge at high pH and
a low charge at low pH. Therefore, these particles can be
effectively used as drug carriers in a drug delivery systems. One
can design the drug release mechanism at both low and high pH,
but this is not possible in the case of a polystyrene particle having
a strong sulfonate group. Apart from this, these particles can also
be self-assembled at higher volume fraction and at higher pH to
form colloidal crystals, which is also very useful for preparing
photonic band gap materials. So far, there have been no reports
on the synthesis, characterization, and study of structural ordering
and dynamics using static and dynamic light scattering. This
motivates us to synthesize polystyrene latex particles having
COO
-
ions on their surfaces and to study their basic properties.
In this article, we will report the synthesis and characterization
of polystyrene-divinyl benzene-acrylic acid copolymer colloidal
particles. The synthesis is carried out according to the general
procedures used by Asher and co-workers.
18-20
They have used
a sulfonated co-monomer such as sodium 1-allyloxy-2-hydroxy-
propane sulfonate (COPS1) to charge the particles. Here we
have used acrylic acid as the co-monomer. We carried out
conductivity titration to determine the dissociable surface charge
number (Z
t
) and conductivity verses particle concentration to
estimate the effective particle charge (Z). The size distribution
was estimated using dynamic light scattering and atomic force
* Corresponding author. E-mail: matsuoka@star.polym.kyoto-u.ac.jp.
†
Kyoto University.
‡
Materials Science Division, Indira Gandhi Centre for Atomic Research.
§
Fuel Chemistry Division, Indira Gandhi Centre for Atomic Research.
(1) Mohanty, P. S.; Tata, B. V. R.; Yamanaka. J.; Sawada, T. Langmuir 2005,
21, 11678.
(2) Matsuoka, H.; Yamamoto, T.; Harada, T.; Ikeda, T. Langmuir 2005, 21,
7105.
(3) Guisheng, P.; Kesavamoorthy, R.; Asher, S. A. Phys. ReV. Lett. 1999, 178,
3860.
(4) Asher, S. A.; Pan, G.; Kesavamoorthy, R. Nonlinear Opt. 1999, 21, 343.
(5) Kamenjicki, M.; Lednev, I. K.; Mikhonin, A.; Kesavamoorthy, R.; Asher,
S. A. AdV. Mater. 2003, 13, 774.
(6) Asher, S. A.; Peteu, S. F.; Reese, C. E.; Lin, M. X.; Finegold, D. Anal.
Bioanal. Chem. 2002, 373, 632.
(7) Wijnhoven, J. E. G. J; Vos, W. L. Science 1998, 281, 802.
(8) van Blaadern, A.; Ruel, R.; Wiltzius, P. Nature 1997, 385, 321.
(9) Sharma, A. C.; Jana, T.; Kesavamoorthy, R.; Shi, L.; Virji, M. A.; Feingold,
D. N.; Asher, S. A. J. Am. Chem. Soc. 2004, 126, 2971.
(10) Holtz, J. H.; Asher, S. A. Nature 1997, 389, 829.
(11) Asher, S. A.; Sharma, A. C.; Goponenko, A. V.; Ward, M. M. Anal.
Chem. 2003, 75, 1676.
(12) Mohanty, P. S. Ph.D. Thesis, Madras University, 2005 (unpublished).
(13) Brown, J. C.; Pusey, P. N.; Goodwin, J. W.; Ottewill, R. H. J. Phys. A:
Math. Gen. 1975, 8, 664.
(14) Tata, B. V. R.; Mohanty, P. S.; Yamanaka, J.; Kawakami, T. Mol. Simul.
2004, 30, 153.
(15) Kesavamoorthy, R.; Tata, B. V. R.; Arora, A. K.; Sood, A. K. Phys. Lett.
1989, 138A, 208.
(16) Pusey, P. N.; van Megen, W. Phys. ReV. Lett. 1987, 59, 2083.
(17) Ha ¨rtl, W.; Versmold, H.; Zhang-Heider, X. J. Chem. Phys. 1995, 102,
6613.
(18) Reese, C. E.; Asher, S. A. J. Colloid Interface Sci. 2002, 248, 41.
(19) Reese, C. E.; Guerrero, C. D.; Weissman, J. M.; Lee, K.; Asher, S. A.
J. Colloid Interface Sci. 2000, 232, 76.
(20) Xu, X.; Friedman, G.; Humfeld, K. D.; Majetich, S. A.; Asher, S. A.
Chem. Mater. 2002, 14, 1249.
4552 Langmuir 2006, 22, 4552-4557
10.1021/la052995a CCC: $33.50 © 2006 American Chemical Society
Published on Web 04/14/2006