Materials Letters 68 (2012) 243–246

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Magnetite nanostructures: One-pot synthesis, superparamagnetic property and

application in magnetic resonance imaging
Shengjian Zhang, Xiaohang Liu, Liangping Zhou, Weijun Peng ⁎
Department of Radiology, Cancer Hospital/Institute & Department of Oncology, Shanghai Medical College, Fudan University, 270 Dong-An Road, Shanghai, 200032, PR China

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

Article history: Diverse magnetite (Fe3O4) nanostructures have been fabricated by a facile, one-pot, economic and environment-
Received 5 September 2011 friendly solvent thermal process simply using ethanol as the solvent, including regular magnetite sub-
Accepted 20 October 2011 micrometer spheres composed of partially ordered array of magnetite nanoparticles, hollow magnetite aggre-
Available online 30 October 2011
gates and monodispersed magnetite nanoparticles. The prepared magnetite nanoparticles possess distinctively
superparamagnetic behavior, showing great potential in biotechnological applications. Importantly, this general
Keywords:
Magnetic materials
synthetic strategy could be extended to prepare other spinel ferrite nanoparticles such as CoFe2O4. A novel hy-
Nanoparticles brid micelle self-assembly mechanism was introduced and demonstrated to explain the formation procedure
Biomaterials of these special nanostructures. Furthermore, the magnetic resonance imaging capability of prepared magnetite
MRI nanoparticles was investigated both in vitro and in vivo.
Solvent thermal © 2011 Elsevier B.V. All rights reserved.

1. Introduction is still a big challenge to tune the assembly of magnetic nanocrystallites

Synthesis of magnetic Fe3O4 nanoparticles has attracted consider-
able attention in the past decade because they show extensively novel
fundamental scientific importance and broad range of technological ap-
plications [1–2]. Various synthetic strategies have been developed to
fabricate Fe3O4 nanoparticles such as chemical co-precipitation, hydro-
thermal process and representative thermal decomposition of iron
complexes (e.g. Fe(CO)5 and Fe(oleate)2) [4–6]. Although the reported
methods have achieved great successes in synthesizing Fe3O4 nanopar-
ticles with tunable sizes and surface nature, the synthetic processes are
generally not environment-friendly and economic. For example, the
usually adopted Fe(CO)5 in the thermal decomposition process is highly
toxic and some expensive agents such as oleylamine and 1-octadece are
necessarily used during the thermal decomposition process [3–4].
Therefore, it is highly desirable to develop a facile, green and economic
synthetic strategy to fabricate Fe3O4 nanoparticles without using ex-
pensive and toxic reagents to satisfy diverse large-scale application
requirements.
In addition, magnetic aggregates and colloidosomes with ordered
or disordered array of nanocrystallites have attracted great attention
recently because of their wide application potentials [5–6]. Some spe-
cial methods such as magnetic field induced self-assembly (MISA) or
evaporation-induced self-assembly (EISA) have been employed to as-
semble the magnetic nanocrystallites into one- or two-dimensional
arrays with meso- and macroscopic scale ordering [5–6]. However, it
into three-dimensional regular aggregates with varied interesting
nanostructures. Herein, we report on a facile, one-pot, low-cost and
environment-friendly synthetic strategies to fabricate Fe3O4 nano-
particles with varied structures such as regular solid/hollow spherical
aggregates and monodispersed small nanoparticles via a simple
solvent-thermal process using ethanol as the solvent. The achieved
Fe3O4 nanoparticles exhibit superparamagnetic property and excellent
magnetic resonance imaging (MRI) capabilities both in vitro and in vivo.
2. Experimental
Synthesis of uniform and regular Fe3O4 nanoparticles with di-
verse nanostructures: 0.9 g of iron stearic acid (Fe(SA)3), 0.6 g of
1,2-dodecanediol and 70 mL of ethanol were mixed and stirred for 3 h
at room temperature. Then the mixture was transferred into a Teflon-
lined autoclave (100 mL capacity), then being sealed and held at
150 °C for 24 h. After the autoclave was cooled down to room tempera-
ture, the precipitate was washed with plenty of ethanol and acetone
several times and dried under vacuum at room temperature overnight.
Hollow Fe3O4 spherical aggregates were obtained using water and eth-
anol as co-solvent (v/v = 3/11) while keeping other synthetic parame-
ters constant. In addition, monodispersed Fe3O4 nanocrystals were
obtained by adding 1 g of polyvinyl pyrrolidone (PVP) in the synthetic
system while keeping other synthetic parameters constant.
3. Results and discussion

⁎ Corresponding author. Tel./fax: + 86 21 64433384. The structure of highly regular and uniform Fe3O4 sub-micrometer
E-mail address: weijunpeng@yahoo.cn (W. Peng). spherical aggregates can be directly visualized from TEM image

0167-577X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2011.10.070
244 S. Zhang et al. / Materials Letters 68 (2012) 243–246
(Fig. 1a). The higher magnification of TEM image (Fig. 1b) indicates
that the Fe3O4 spherical aggregates are composed of array of small
Fe3O4 nanoparticles (about 5 nm in size). These small magnetite
nanoparticles are arrayed with partial ordering, demonstrated by
the honeycomb-like structure (Fig. 1b). The wide-angle X-ray diffrac-
tion pattern is assigned to identify the crystal phase of Fe3O4 spherical
aggregates. The pattern (Fig. S1) is assigned to the (220), (311), (400),
(422), (511) and (440) reflections of the cubic spinel structure of Fe3O4
(JCPDS no. 19-0629), which is also supported by selected area electron
diffraction and Raman spectrum (Figs. S2 and S3). The mean crystallite
size of small Fe3O4 nanoparticles determined by Debye–Scherrer for-
mula is about 5 nm, in consistence with TEM observations.
Interestingly, by adopting the mixture of water and ethanol as the
co-solvent, the hollow structured Fe3O4 aggregates can be fabricated.
From TEM images (Fig. 1c and d), we can clearly observe the hollow
structures according to the clear contrast difference between interior
core and outer shell. This interesting hollow structure is considered
to be attributed to the partial presence of H2O, as water droplets can
be formed under autogenous pressure at 150 °C at the first stage,
then Fe3O4 nanocrystallites adsorb on the surface of droplets to reduce
the total surface energy to form hollow core/shell structure (Fig. S4),
which is similar to the formation of “colloidosomes”. Importantly, by
adding PVP molecules in the synthetic systems, highly dispersed
Fe3O4 nanoparticles with crystallite nanostructures could be obtained
(Fig. 1e and f).
A hybrid micelle self-assembly process have been developed to ex-
plain the whole formation procedure for these unique Fe3O4 nanostruc-
tures (detail discussions and Fig. S5, see supporting information), which
was also further demonstrated by employing different iron precursors
with variable carbon chains (Fe(SA)3 and Fe(OA)3, Fig. 2). Importantly,
CoFe2O4 aggregates can also be obtained using Co(SA)2 and Fe(SA)3 as
co-precursor (Fig. S6) with mole ratio equal to 1:2 showing the generality
Fig. 1. TEM images of solid (a and b) and hollow (c and d) Fe3O4 spherical aggregates, and monodispersed Fe3O4 nanoparticles (e and f) with different magnifications.
of this method to fabricate MFe2O4 (M=Fe, Co, Mn, Cu, Zn, Ni et al.)
spherical aggregates, which makes the further modulation of magnetic
properties possible.
The magnetic nature of solid Fe3O4 spherical aggregates is character-
ized by M-H hysteresis loop behavior at 300 K by cycling the field be-
tween −20 and 20 kOe. The sub-micrometer sized Fe3O4 aggregates
exhibit superparamagnetic behavior with the saturation magnetization
(Ms) of 7 emu g− 1 at room temperature, which is indicated by the neg-
ligible remanence or coercivity in the hysteresis curve (Fig. 3a). The
temperature dependence of the ZFC/FC magnetization is shown in
Fig. 3b. Two curves coincide at higher than 25 K and begin to separate
below the temperature, which is the representative characteristic of
superparamagnetism. Interestingly, the blocking temperature (TB) of
the Fe3O4 spherical aggregates is only 16.5 K, much lower than those
reported previously about conventional magnetic aggregates [7]. Com-
pared to previous report on the large sized spherical Fe3O4 nanocrystal-
lite without the aggregate structure [8], where the materials showed
significant remnant Mr of 7.0 emu/g and coercivity Hc of about 44 Oe,
the present spherical aggregates are the pure superparamagnet due to
separating effect between the nanocrystallites by the long carbon chains
on the crystallite surface as the shell of the hybrid micelles. Such a super-
paramagnetic property is very useful for biomedical applications [1].
To reveal the potential application of prepared Fe3O4 nanoparticles
(monodispersed nanoparticles and solid aggregates, Figs. 4 and S7) as
the contrast agents for MR imaging, the MRI assess of magnetite nano-
particles on a clinical MRI instrument at 3 T was carried out. The Fe3O4
nanoparticles were transformed from hydrophobic phase into aqueous
solution by the assistance of clinically used Tween 80. As shown in
Fig. 4a, the T2 value dropped significantly with the increase of Fe3O4 con-
centrations. Besides, the transverse (T2) phantom images of Fe3O4 nano-
particles at different concentrations in water change significantly in
signal intensity (inset of Fig. 4a), demonstrating that Fe3O4 nanoparticles
 S. Zhang et al. / Materials Letters 68 (2012) 243–246 245

Fig. 2. TEM images of (a) Fe3O4 spherical aggregates and (b) circle marked area in a with high magnification, and TEM image of Fe3O4 spherical aggregates with high magnification
(Fe3O4 structures in a, b and c were obtained employing Fe(AC)3 as the iron precursor); (d) TEM image of Fe3O4 spheres obtained by using Fe(OA)3 as the iron precursor.

have generated magnetic resonance contrast on T2 proton relaxation-

time-weighted sequences due to the dipolar interaction of the magnetic
moment of the particles and protons in water [1]. The in vivo T2 value of
MR imaging of the mouse liver changes substantially (Fig. 4b and c, from
420 ms before administration to 298 ms after 30 min of intravenous ad-
ministration), demonstrating the excellent MR imaging capability of pre-
pared magnetite nanoparticles for the diagnosis of liver abnormities.

4. Conclusions

In summary, a facile, one-pot, economic and environment-friendly

solvent hydrothermal method has been developed to fabricate Fe3O4

Fig. 4. (a) T2 values of Fe3O4 monodispersed nanoparticles in aqueous solution with

Fig. 3. Magnetic measurements of solid spherical Fe 3O4 aggregates obtained using different concentrations (inset: T2 phantom images), and in vivo MR images of mouse
Fe(SA)3 as iron precursor showing (a) magnetization-applied magnetic field (M-H) liver before (b) and after (c, 30 min) intravenous injection of Fe3O4 nanoparticle saline
and (b) zero-field-cooled (ZFC) and field-cooled (FC) magnetization curves. solution.
246 S. Zhang et al. / Materials Letters 68 (2012) 243–246
nanoparticles with diverse interesting structures, including highly
regular and uniform solid/hollow Fe3O4 aggregates and monodispersed
Fe3O4 nanoparticles. Importantly, this general synthetic strategy could
be extended to prepare other spinel ferrite nanoparticles such as
CoFe2O4. The prepared Fe3O4 nanoparticles possess extraordinary super-
paramagnetic properties and show the great potential as contrast agents
in clinical MR imaging, which was demonstrated both in vitro and in vivo.
Acknowledgment
We greatly acknowledge Dr. Y. Chen and Prof. J. L. Shi for their
kind advice and assistance, and the financial support of by the Opening
Project of State Key Laboratory of High Performance Ceramics and
Superfine Microstructure (Grant No. SKL201106SIC).
Appendix A. Supplementary data
Supplementary data to this article can be found online at doi:10.
1016/j.matlet.2011.10.070.
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