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DOI 10.1007/s00396-005-1383-5
F. Sayar
G. Guven
E. Pis kin
ORIGINAL CONTRIBUTION
Abstract Magnetically loaded polymeric nano-particles carrying functional groups on their surface were
prepared by a two-stage process. In
the rst stage, super-paramagnetic
magnetite (Fe3O4) nano-particles
were produced by a co-precipitation
method from the aqueous solutions
of FeCl24H2O and FeCl36H2O
using a NaOH solution. The smallest
size obtained was 40.9 nm with polydispersity index of 0.194 obtained by
using a Zeta Sizer. The eects of
Fe2+/Fe3+ molar ratio, stirring rate,
temperature, base concentration,
and pH on the particle size/size distribution and stability of the dispersions were examined. Increasing the
relative concentration of Fe2+ ion
and decreasing the stirring rate and
pH increased the particle size, while
the concentration of NaOH and
temperature did not change the
particle size signicantly. Polymer
coating was achieved by emulsion
polymerization at high surfactant to
Introduction
Magnetic colloidal nano-particles are increasingly used
in bio-separation, in biosensor, and in diagnosis and
therapy in medicine including immunoassays, medical
imaging and targeted drug delivery [15]. Several kind of
magnetic polymer nano-particles, which are usually
dispersed in a carrier liquid (usually water), therefore
called also as latex, with tailor-made properties
depending on the nal application have been produced
from both natural and synthetic polymers [2, 610].
966
967
reactor containing 160 ml distilled water at 80 C under N2 atmosphere, by vigorous agitation. The black
precipitate was formed at the early phase, but the
medium was continuously stirred for 2 h at a given
stirring rate and temperature followed by the slow
addition of 10 ml 25% (w/w) TMAOH to stabilize the
magnetite particles.
Synthesis of magnetic polymeric nano-particles
Temperature (C)
pH
M1
M2
M3
M4
M5
M6
M7
M8
M9
M10
M11
M12
M13
M14
M15
M16
M17
M18
M19
M20
0.5
1.0
1.5
2.0
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
3,000
3,000
3,000
3,000
1,000
1,500
2,000
3,000
2,000
2,000
2,000
2,000
2,000
2,000
2,000
2,000
2,000
2,000
2,000
2,000
80
80
80
80
80
80
80
80
20
40
60
80
80
80
80
80
80
80
80
80
5
5
5
5
5
5
5
5
5
5
5
5
2.5
5.0
7.5
10.0
5
5
5
5
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
12
3
6
9
12
968
Surfactant type
Initiator type
Conc. (mM)
Magnetite/monomer
ratio (wt%)
Surfactant/monomer
ratio (wt/wt)
P1
P2
P3
P4
P5
P6
P7
P8
P9
P10
P11
P12
P13
P14
P15
SDS
CTAB
DTAB
SDS
SDS
SDS
SDS
SDS
SDS
SDS
SDS
SDS
SDS
SDS
SDS
KPS
KPS
KPS
KPS
AIBN
V-50
KPS
KPS
KPS
KPS
KPS
KPS
KPS
KPS
KPS
1.5
1.5
1.5
1.5
1.5
1.5
1.5
2.0
2.5
1.5
1.5
1.5
1.5
1.5
1.5
25
25
25
25
25
25
25
25
25
5
25
50
25
25
25
1.47
1.47
1.47
1.47
1.47
1.47
1.47
1.47
1.47
1.47
1.47
1.47
1.11
1.47
2.94
a
The monomer concentration, polymerization temperature, and polymerization time were 6.34% wt, 65C, and 24 h, respectively, in all
these experiments.
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Magnetite nano-particles
Particle size and size distribution of magnetite
nano-particles
The average particle size and size distribution of the
magnetite nano-particles prepared in the rst step were
measured by Zeta Sizer. Table 3 gives these values obtained at dierent conditions. Note that in each group
only one parameter was changed (given in bold in Table 3) the others were the same (see Table 1 for recipe).
The average particle size was an average of minimum 30
measurements, and the size distributions (or the socalled PDI) were recorded automatically by the software
of these repeated measurements.
Eects of Fe2+/Fe3+ mole ratio
In this study, Fe2+/Fe3+ ratio in the initial mixture
was selected as one of the parameters, which is eective on the particle size of magnetite nano-particles to
be produced by co-precipitation following the statements given in the related literature [1517]. The
chemical reaction of magnetite precipitation is expected as follows:
Experiment no.
Fe2+/Fe3+ ratio (mol/mol)
M1
M2
M3
M4
Stirring rate (rpm)
M5
M6
M7
M8
Temperature (C)
M9
M10
M11
M12
NaOH Conc. (M)
M13
M14
M15
M16
pH
M17
M18
M19
M20
Average particle
size (nm)
Particle size
distribution (PDI)
0.5
1.0
1.5
2.0
40.9
91.6
112.3
130.0
0.194
0.326
0.308
0.577
1,000
1,500
2,000
3,000
325.6
224.9
130.7
61.9
0.637
0.414
0.517
0.256
20
40
60
80
130
136.7
145
150.2
0.234
0.294
0.326
0.341
2.5
5.0
7.5
10.0
148.5
143
138.2
134.9
0.520
0.324
0.317
0.414
3
6
9
12
391
274.7
217.4
134
0.167
0.153
0.362
0.335
970
971
Eects of pH
972
Table 4 Summary data of experimental d (exp) (A) spacing obtained from the X-ray patterns and from ASTM data cards [8] for
iron oxide (d (Fe3O4))
2h (exp)
d (exp)
d (Fe3O4)
17.460
30.200
56.720
62.500
5.07
2.96
1.62
1.48
4.852
2.099
1.615
1.484
973
Experiment no.
Initiator type
P4
P5
P6
KPS concentration (mM)
P7
P8
P9
Average particle
size (nm)
Particle size
distribution (PDI)
KPS
AIBN
V-50
125.2
150.0
148.8
0.193
0.218
0.273
1.5
2.0
2.5
151.9
130.1
125.2
0.217
0.195
0.183
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Experiment no.
Magnetite (Fe3O4) /monomer
P10
P11
P12
KPS concentration (mM)
P13
P14
P15
ratio (wt%)
5
25
50
1.11
1.47
2.94
Average particle
size (nm)
Particle size
distribution (PDI)
136.5
125.2
120.9
0.300
0.183
0.158
159.7
125.2
117.5
0.251
0.183
0.206
975
976
Fig. 5 Representative magnetization curves: (a) magnetite nanoparticles (Fe3O4); (b) magnetic nano-particles (containing 25%
Fe3O4)
b
c
Tm (C)
Tdecom (C)a
117.7
195210 (225395)
208.7
977
Conclusions
Super paramagnetic poly(MMA/AAc-90/10) nano-particles were synthesized in situ via two steps: (1) preparation of magnetite (Fe3O4) nano-particles by coprecipitation method and (2) emulsion polymerization at
high surfactant/monomer ratio of MMA and AAc
monomers in the presence Fe3O4 nano-particles. Studies
on particle size and size distribution of the magnetite
nano-particles revealed that the change in Fe2+/Fe3+
molar ratio, stirring rate, and pH plays an important
role in controlling the particle size and magnetic property. On the other hand, the concentration of NaOH and
temperature does not aect the size signicantly. The
smallest size obtained was 40.9 nm. Conventional
emulsion polymerization at high surfactant/monomer
ratio technique was used for the coating of the magnetite
nano-particles with this size. The results showed that
SDS and KPS are the most convenient surface active
agent and initiator for this system. Depending on the
reaction parameters the size range obtained was between
115 and 300 nm for the polymer-coated nano-particles.
Increasing magnetite, surfactant content, and KPS
concentration decreased the particle size. Zeta potential
of the smallest particle was )20.1 mV, which indicates
the carboxylic acid groups on the particle surfaces.
These magnetically loaded polymeric nano-particles did
not loose their magnetic property after the coating. They
still showed super-paramagnetic property. Applications
of these novel magnetically loaded polymeric nanoparticles for diverse biomedical applications including
electrochemical-based DNA sensors and separation/
purication of stem cells are under investigation.
Acknowledgement Prof. Erhan Piskin was supported by Turkish
Academy of Sciences as a full member.
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