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Synthesis and Characterizations of Surface-Coated Superparamagentic

Magnetite Nanoparticles

Article in IEEE Transactions on Magnetics · March 2010

DOI: 10.1109/TMAG.2009.2033205 · Source: IEEE Xplore

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IEEE TRANSACTIONS ON MAGNETICS, VOL. 46, NO. 2, FEBRUARY 2010 443

Synthesis and Characterizations of Surface-Coated Superparamagentic

Magnetite Nanoparticles
Yu-Jung Cha1 , Min-Jung Kim2 , Yong-Ho Choa2 , Jongryoul Kim3 , Baekil Nam1 , Joonsik Lee1 ,
Dong Ho Kim1 , and Ki Hyeon Kim1
Department of Physics, Yeungnam University, Gyeongsan 712-749, Korea
Department of Chemical Engineering, Hanyang University, Ansan 426-791, Korea
Department of Metallurgy and Materials Engineering, Hanyang University, Ansan 426-791, Korea

The uncoated magnetite and the 2, 3-meso-dimercaptosuccinic acid (DMSA)-coated Fe3 O4 nanoparticles were synthesized by a co-
precipitation method, respectively. The DMSA surface modification on magnetite nanoparticles was observed by FT-IR. The average
particle sizes of the uncoated magnetite and the DMSA coated magnetite were exhibited approximately 10.4 and 12.3 nm by TEM results.
DMSA surface-coated Fe3 O4 can introduce a dense and thin outer hydroxyl group ( OH) shell. In order to characterize the magnetic
behaviors, the magnetization processes of the magnetic nanoparticles were measured with the temperature range of 5 K to 300 K. The
mean blocking temperatures of the uncoated Fe3 O4 and the DMSA surface-coated Fe3 O4 exhibited about 172 28 K and 215 30 K,
respectively. The value of magnetization of the DMSA-coated Fe3 O4 nanoparticles was not so different with that of the uncoated Fe3 O4 .
Index Terms—Magnetic particle, magnetite, magnetization, polymer, superparamagnetic.

I. INTRODUCTION

UMEROUS magnetic nanoparticles with various chem-

N ical compositions have been proposed and evaluated
for biomedical applications to exploit nanoscale magnetic
phenomena, such as enhanced magnetic moments and super-
paramagnetism. Composition, size, morphology, and surface
chemistry can now be tailored by various processes to improve
the magnetic properties in biocompatibility [1]–[6]. With
proper surface coating, these magnetic nanoparticles can be
dispersed into suitable solvents, forming homogeneous sus- Fig. 1. (a) Experimental procedure of Fe O . (b) DMSA surface-coated mag-
pensions, called ferrofluids [4], [9], [10]. Such suspensions of netite nanoparticles.
superparamagnetic iron oxide nanoparticles and their surface
modification have been employed in numerous biomedical
applications such as magnetic resonance imaging contrast surface of the ferric oxide particles. Negative surface charges
enhancement, cell sorting or separation, tissue repair, drug de- resulting from the acid-base behaviors of grafted DMSA cause
livery and hyperthermia, etc. [4], [5], [8], [11]–[13]. For these repulsive particle interactions and prevent aggregation [12].
applications, the particles must have the following properties Also, DMSA has many advantages without the drawbacks of
of high magnetic saturation, biocompatibility, and interactive toxicity and redistribution of toxic elements to other organs
functions at the surface. The surfaces of these particles could be and tissues as well as the specificity for heavy metals such
modified through the creation of a few atomic layers of organic as lead, mercury, cadmium, gold, platinum, thallium, barium,
polymers or inorganic metallic (e.g., gold) or oxides (e.g., silica and strontium. Under aqueous solution, the thiol groups and
or alumina), suitable for further functionalization to attach carboxylic acid group from DMSA are stable and do allow a
various bioactive molecules [7], [14]. The surface-modified direct functionalization without storage in stringent conditions
iron-oxide beads are generally of core-shell type: The biolog- or a chemical regeneration.
ical species cells, nucleic acids, and proteins are connected Therefore, we synthesized and characterized the Fe O
to the magnetite core through an organic or polymeric shell. nanoparticles and the surface-modified Fe O nanoparticles by
Therefore, the investigation of magnetite nanoparticles with the thiol groups and carboxylic acid group of DMSA.
organic coatings is very important for biomedical applications
[15].
Especially, DMSA (meso-2,3-dimercaptosuccinic acid or II. EXPERIMENTAL PROCEDURE
succimer) as one of surface-coating materials interacts with the The magnetite nanoparticles were synthesized by using a
coprecipitation method as shown in Fig. 1. FeCl 4H O and
Manuscript received June 20, 2009; revised August 31, 2009; accepted FeCl 6H O ( molar ratio) were dissolved
September 21, 2009. Current version published January 20, 2010. Corre- in deionized water under nitrogen gas with vigorous stirring at
sponding author: K. H. Kim (e-mail: [email protected]). 80 C to prevent oxidation. Then, the magnetite nanoparticles
Color versions of one or more of the figures in this paper are available online
at http://ieeexplore.ieee.org. were obtained by adding NH OH as a precipitator. The 0.8-mol
Digital Object Identifier 10.1109/TMAG.2009.2033205 DMSA was diluted with DMSO (dimethylsulfoxide).
0018-9464/$26.00 © 2010 IEEE
444 IEEE TRANSACTIONS ON MAGNETICS, VOL. 46, NO. 2, FEBRUARY 2010

Fig. 2. FT-IR spectra of (a) uncoated magnetite particles and (b) DMSA-coated
magnetite particles, respectively. Fig. 3. X-ray diffraction patterns of (a) Fe O and (b) DMSA-coated magnetite
particles, respectively.

One gram of Fe O nanoparticles was added into 10 mL of

the DMSA solution with stirring in an air atmosphere for 24 h.
The particle morphology was determined by using high-reso-
lution transmission electron microscopy (HRTEM: JEM-300F,
JEOL, Japan). X-ray powder diffractometer, FT-IR (FTS6000,
BIO-RAD, USA), and Dynamic Light Scattering (DLS) were
used to characterize the structure, composition, and size distri-
bution of the magnetite and the modified magnetite nanoparti-
cles. The magnetic properties of the nanoparticles were mea-
sured by using Physical Property Measurement System (PPMS
6000, Quantum Design).

III. RESULTS AND DISCUSSIONS

The polymerization process of the DMSA-coated magnetite
nanoparticles was proven by FT-IR spectra in comparison
to those of uncoated magnetite nanoparticles. Fig. 2 shows
the FT-IR spectra of (a) the uncoated magnetite particles and Fig. 4. TEM images of (a) the uncoated Fe O magnetic particles and (b) the
surface-coated Fe O magnetic particles by DMSA and DLS histograms for
(b) DMSA-coated magnetite particles. All the samples have magnetic particle size distributions (c) before and (d) after modification by
characteristic absorption band of the Fe-O bond of Fe O at DMSA, respectively.
572 cm [16]. In Fig. 2(b), the FT-IR spectrum of the surface
modified Fe O with DMSA shows a strong band at 1011 cm
attributed to the C-O ether stretch. In addition, these possess the the DLS histograms of size distribution for the uncoated mag-
absorption bands 1396 cm and 2988 cm due to stretching netite and the DMSA-coated magnetite were 10.4 and 12.3 nm,
vibration of the bond and the S-H bond, respectively. respectively, as shown in Fig. 4(c) and (d). It can be predicted
The results indicate that DMSA is successfully bound to the that the minimum thickness of coated DMSA shell on magnetite
surface of Fe O nanoparticles. nanoparticles was about 10 .
To analyze the crystalline structure, the X-ray diffraction Fig. 5 shows the temperature dependence of the zero-field-
patterns for the uncoated magnetite nanoparticles and the cooled (ZFC) and field-cooled (FC) magnetizations measured in
DMSA-coated magnetite nanoparticles were obtained as shown a field of 300 Oe, respectively. The ZFC magnetization curves
in Fig. 3(a) and (b). Although DMSA was coated on magnetite, show the broad maximum at about K and K for
there is no different Fe O crystalline structure between the the uncoated and the DMSA-coated magnetite nanoparticles, re-
uncoated magnetite and surface coated magnetite nanoparti- spectively. The flatness of the FC curves suggests the existence
cles, representing that the surface-coated DMSA did not affect of magnetic interactions among particles [16], [17]. The max-
the crystalline structure of the magnetite core particles, which imum in the ZFC curve defines the blocking temperatures ,
means the Fe O nanoparticles were stable even after surface where the thermal energy becomes comparable to the anisotropy
modification. energy barrier. It is well known that the superparamagnetism
In order to investigate the morphology and the size distri- becomes thermally unstable above blocking temperature. The
butions, the images and the size distributions of nanoparticles blocking temperature depends on the volume of the particle ac-
were obtained by using TEM and DLS, respectively, as shown cording to the relation [19]–[21], where
in Fig. 4. The uncoated magnetite nanoparticles and the DMSA- is the effective anisotropy constant, is the average volume of
coated magnetite nanoparticles were spherically well dispersed the particle, and is the Boltzman constant. Considering that
as shown in Fig. 4(a) and (b). The observed average diameters by the magnetic particles are spherical, the values of can be
CHA et al.: SYNTHESIS AND CHARACTERIZATIONS OF SURFACE-COATED SUPERPARAMAGENTIC MAGNETITE NANOPARTICLES 445

where is the temperature-dependent magnetization,

is the Bloch constant, and is the Bloch exponent. The inset
of Fig. 6(c) shows the best fit of data to (1), leading to
K , and K
, for the uncoated Fe O and the DMSA-coated Fe O
nanoparticles, respectively. Bloch exponent for the DMSA-
coated Fe O nanoparticles is less than that of the uncoated
Fe O . Bloch exponent decreases with the decrease in particle
size, which is reported earlier in the case of nano-sized iron par-
Fig. 5. Magnetization (M) versus temperature (T) measured in the ZFC and ticles [22]. These results coincide with those of estimations by
the FC modes at 300 Oe of (a) the uncoated Fe O nanoparticles and (b) the
DMSA-coated Fe O nanoparticles, respectively.
calculated effective anisotropy constant. It implies that these be-
haviors are believed to be due to the presence of a dead layer
between the core magnetite and the DMSA shell. The coerciv-
ities increased exponentially below and decreased to nearly
zero with the increase of temperature above as expected, as
shown in Fig. 6(d). For noninteracting magnetic nanoparticles,
the coercivities as a function of temperature, below the block
temperature, follows the linear relation [20]

(2)

For the present nanoparticles, the variation of as a func-

tion of is found to be nonlinear, indicating the highly inter-
acting nature of the nanoparticles. The variation of the coercivity
with the temperature is found to follow an exponential relation
[23]

(3)
Fig. 6. The comparison of the magnetization curves measured from 300 K to
5 K for (a) the uncoated Fe O nanoparticles and (b) the DMSA-coated Fe O where is the coercivity at 0 K and is constant. From
nanoparticles. (c) The change of magnetizations at 30 kOe and (d) the coercivi- fitting to the logarithmic equation, were obtained as
ties values (Inset: exponential decay of the coercivity with increasing tempera-
ture and fitted curves) with the function of temperature for the uncoated Fe O 187 Oe, 0.019 K and 198.7 Oe, 0.021 K for uncoated
nanoparticles and the DMSA-coated Fe O nanoparticles, respectively. Fe O and the DMSA-coated Fe O nanoparticles, respec-
tively, as shown in Fig. 6(d). These observed behaviors have
been explained in terms of random dipolar interactions or
calculated as erg/cm and erg/cm for each exchange fluctuations among the short-range-ordered magnetic
of the uncoated Fe O and DMSA-coated Fe O nanoparti- clusters.
cles, respectively. The values of generally increase with the Assuming that the sample consists of noninteracting single-
decreasing particle size due to the degree of disorder in the ferric domain particles, in the superparamagnetic state, the magneti-
oxide structure, which is governed by contributions from surface zation is described by the Langevin function [20]
anisotropy, strong interparticle interactions, etc. It means that
the average magnetic core particle size of DMSA-coated mag- (4)
netite is a little bit smaller than that of the uncoated magnetite
nanoparticles. Therefore, it would be predicted that the -Fe O where represents the saturation magnetization, and
phase would exhibit the phase deformation in interface layer be- , with being the magnetic moment of the nanoparti-
tween the core and the shell of DMSA-coated Fe O nanopar- cles defined as . The average magnetic-particle diam-
ticles. eter can be obtained by fitting the slope of magnetization near
The measured magnetization curves with the change of the zero-field region, from the magnetization curves
temperature from 5 K to 300 K are shown in Fig. 6(a) and (b), at 300 K. The average particle diameter is estimated by using
which exhibited the typical superparamagnetic behavior above the following relation [24], [25]:
, as already shown in Fig. 5. The measured and theoretical
fitting results of saturation magnetizations as a function of tem- (5)
perature are shown in Fig. 6(c). The magnetizations decreased
with the increase of the temperature. The thermal dependence where is the density (the densities of magnetite and maghemite
of can be fitted to the following equation: phases are generally given in the range of 4.9 to 5.2 g/cm )
[6], [23]. Fig. 7(a) and (b) show the measured magnetization
(1) curves and fitting results by (4) at 300 K for the uncoated Fe O
446 IEEE TRANSACTIONS ON MAGNETICS, VOL. 46, NO. 2, FEBRUARY 2010

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