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ARTICLE

Synthesis of Amphipathic Superparamagnetic Fe3O4 Janus

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Nanoparticles via a Moderate Strategy and Their Controllable Self-

RSC Advances Accepted Manuscript

Received 00th February 20xx,
assembly
Accepted 00th February 20xx
Wenliao Li, Xiaojun Cai, Shaohua Ma, Xiaohui Zhan, Fang Lan, Yao Wu*, Zhongwei Gu
DOI: 10.1039/x0xx00000x
Abstract: Recently, amphipathic Janus Fe3O4 nanoparticles, with distinct hydrophilic and hydrophobic “faces”, have attracted
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tremendous attention. However, conventional synthesis methods for these nanoparticles either influenced the
superparamagnetism of Fe3O4 nanoparticles or failed to endow Fe3O4 nanoparticles evident amphipathy, and thus as-
prepared amphipathic Janus Fe3O4 nanoparticles hardly reveal remarkable self-assembly properties. To address these critical
issues, a versatile strategy that combines activators regenerated by electron transfer for atom transfer radical
polymerization (ARGET-ATRP) and Pickering emulsions is proposed here to synthesize amphipathic Janus Fe3O4 nanoparticles
for the first time. Owing to the masterly integration all of the unique features of ARGET-ATRP and Pickering emulsions, Janus
Fe3O4 nanoparticles with high saturation magnetization and diverse self-assembly behaviors in different solvents are
successfully prepared in a gentle, simple and highly controllable reaction condition. Furthermore, these Janus Fe3O4
nanoparticles exhibit prominent emulsification in toluene-water model system as their superior amphipathy. These
emulsions could not only maintain excellent stability even in an extremely low usage of Janus Fe3O4 nanoparticles, but also
be easily separated by an external magnetic field because of the intrinsic superparamagnetism of Fe3O4. The result implies
that the as-received Janus Fe3O4 nanoparticles may have extensive application prospects in oil purification from oil-water
compounds. This synthesis strategy likewise could be a guidance to synthesize similar Janus materials.

increased substantially over the last few years.13-16 Therefore,

1 Introduction
In recent years, functionalized superparamagnetic Fe3O4
nanoparticles have been widely utilized in many promising fields
such as magnetic resonance imaging (MRI), biomedical separation,
drug delivery, self-propellers, emulsifiers etc.1-5 However, most of
them have no option for selective modification at some specific
sites,6-8 which makes chaotically modified functional groups interfere
with each other to reduce activities or leading to unfavourable
structural and chemical arrangements of these functional
components. In this regard, Janus Fe3O4 nanoparticles have been
deemed a potential alternative because of their excellent anisotropy
in composition, shape, and surface chemistry.9-12 Noteworthy,
among all Janus categories, studies of amphipathic Janus Fe3O4
nanoparticles, known as representative of anisotropy particle, have
National Engineering Research Center for Biomaterials, Sichuan University,
Chengdu, 610064, China Email: wuyao@scu.edu.cn
Electronic Supplementary Information (ESI) available: TEM images and XRD of
hydrophilic Fe3O4 nanoparticles, visual evaluation images of Fe3O4 nanoparticles
and Fe3O4/wax composite microsphere, FTIR spectrum of Fe3O4 nanoparticles
and Janus Fe3O4 nanoparticles, High-resolution TEM images of Janus Fe3O4
nanoparticles, DLS of J-NPs with different PMMA polymerization degree
assembly in water, Janus Fe3O4 nanoparticles emulsification application.
See DOI: 10.1039/x0xx00000x
developing the sort of amphiphilic Janus Fe3O4 nanoparticles is of
significance and challenging.
The past decade have witnessed many efforts working on
methods for fabricating Janus Fe3O4 particles with distinct
hydrophilic and hydrophobic “faces”, including electrostatic
adsorption, phase separation method etc.17-20 These scanty methods
gained some progress in fabricating the Janus Fe3O4 nanoparticles
with hydrophilic-hydrophobic polymer brushes in opposite domains.
However, certain defects lying in these methods can’t be neglected
either. For example, in electrostatic adsorption process, although
changing pH is essential to adsorb and separate Fe3O4 nanoparticles
from substrate, infinitely destroy the superparamagnetism of Fe3O4
nanoparticles since Fe3O4 is easy to be corroded by H+.18,19 In phase
separation method, as-prepared Janus Fe3O4 nanoparticles failed to
demonstrate apparent amphipathy as well as controllable self-
assembly morphology in solvent.20 Overall, these methods resulted
in the decrease of saturation magnetization sharply. Consequently,
establishing a novel method is desideratum to prepare Janus Fe3O4
nanoparticles with splendid superparamagnetism and distinct
amphipathy.
Recently, the combination of Pickering emulsions approach and
polymer grafting has begun to be proposed to fabricate Janus
particles from the sub-micrometer range to several micrometers.21-

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95 ℃
Paraffin
High Stir
Water
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Hydrophilic Fe3O4 NPs
Fe3O4-Br NPs
Amphiphilic Fe3O4 NPs
PMMA
Scheme 1. Schematic Illustration for the Synthesis of Amphiphilic Janus Fe3O4 nanoparticles.
23 This scheme based on two phases (normally, an emulsion of
molten wax and water), first generated an interface to absorb,
stabilize and decorate plentiful particles, and then masses of the
decorated particles were respectively modified with hydrophilic-
hydrophobic polymer to obtain the amphipathic Janus particles via
the polymer grafting method.21,22 For example, Granick et al, firstly
reported the synthesis of amphipathic Janus SiO2 microparticles via
combining the Pickering emulsions method and “graft to”
approach.21 Whereas, since the limitation of “graft to” method, the
amphipathy of the as-prepared Janus particles haven’t been well
controlled. Luckily, this problem has been addressed to some extent
by Synytska et al via the combination of atom transfer radical
polymerization (ATRP) and Pickering emulsions.22,23 Nonetheless,
this wax immobilization approach is extremely limited to produce
Janus nano-scale particles. Different from the microparticles, just
because the absorption energy of nanoparticles is comparable with
thermal energy, multiple layer nanoparticles aggregation will more
likely to occur on the wrinkled interface in case of nanoparticles
employed into the Pickering emulsions processing.15 Meanwhile,
ATRP has rigorous experimental conditions and intricate reaction
process etc. drawbacks.24-28
Currently, the activators regenerated by electron transfer for
atom transfer radical polymerization (ARGET-ATRP) has been
increasingly used in the synthesis of polymers, since it offers plentiful
principle advantages over conventional ATRP: improved tolerance of
oxygen significantly, reduced heavy metal catalyst concentrations,
required mild reaction conditions and simple experimental setup, as
well as achieved exquisite controllability.29-31 On the other hand, it’s
well known that the surface properties of nanoparticles are very
critical to influence the stabilization and aggregation during the
Pickering emulsions processing. Polyol process prepared Fe3O4
nanoparticles with lots of inherent superiorities, such as water
solubility, high magnetization, as well as minimal thermal energy,32,33
could efficiently prevent the interparticle aggregating during the
formations of emulsion in Pickering emulsions.
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DOI: 10.1039/C6RA04648G
BrCH2COOH
Ligand
Exchange
Chloroform
RSC Advances Accepted Manuscript
PMMA
ARGET-ATRP
Accordingly, in this study, taking use of the polyol prepared
hydrophilic Fe3O4 nanoparticles, we firstly proposed a novel and
versatile strategy combined of Pickering emulsions and ARGET-ATRP
to prepare the Janus Fe3O4 nanoparticles with excellent
superparamagnetism in a gentle, simple and highly controllable
reaction method. (Scheme 1) Interestingly, we found that
homogeneous and stable Fe3O4/wax emulsions could be formed and
remain stable in water. Hydrophobic poly (methyl methacrylate)
(PMMA) brush could be controllably grafted on the surface of Fe3O4
nanoparticles in a mild condition. With the controllable adjustment
of PMMA polymerization degree in ARGET-ATRP processing, the
prepared Janus Fe3O4 nanoparticles with very satisfied saturation
magnetization exhibited distinct amphipathy and diversiform self-
assembly morphology in different solvents. Furthermore, these
Janus Fe3O4 nanoparticles demonstrated prominent emulsification in
toluene-water model system as their superior amphipathy. These
emulsions could not only maintain excellent stability even in an
extremely low usage of Janus Fe3O4 nanoparticles, but also be easily
separated by an external magnet, which implied that the synthesized
Janus Fe3O4 nanoparticles might have extensive application
prospects in oil purification from oil-water compounds. This strategy
of preparation of Janus magnetic materials can also be a guidance to
prepare nano-scale anisotropic materials.
2 Experimental section
2.1 Materials.
Sodium ascorbate, copper bromide (CuBr2), N,N,N’,N”,N”-
pentamethyldiethylenetriamine (PMDETA), bromoacetic acid, pyren-
1-ylmethyl methacrylate, Fe(acac)3, and triethylene glycol (TEG) were
all purchased from Sigma-Aldrich and used without further
purification. All other chemicals, such as anhydrous ethanol,
chloroform, wax, methylbenzene, methyl methacrylate (MMA, 99%),
and toluene were of analytical grade and were obtained from
commercial sources.
2.2 Synthesis of Janus Fe3O4 nanoparticles.
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2.2.1 Synthesis of the hydrophilic Fe3O4 nanoparticles
Hydrophilic superparamagnetic Fe3O4 nanoparticles were prepared
via the polyol method.33 Briefly, 720 mg of Fe(acac)3 and 40 mL of
TEG were mixed in a three-necked flask by magnetic stirring. Then,
the flask was vacuumized and infiltrated with nitrogen for three
times. The resulting mixture was first heated to 180 ℃ for 30 min
and then heated to 280 ℃ for refluxing for another 30 min. After
cooling to room temperature, a black homogeneous magnetic
suspension was obtained.
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2.2.2 Synthesis of Fe3O4/wax composite microsphere
Following the theory of Pickering emulsions, homogeneous
emulsions of Fe3O4/wax were first obtained by addition of molten
paraffin wax (270 mg) and 10 mL of ultrapure water to Fe3O4
suspension (5 mL) under mechanical stirring for 1.5 h at 95 ℃. Then
the homogeneous emulsions were cooled to room temperature,
followed by washed with ethyl alcohol for several times to remove
the non-magnetic particles and weakly attached magnetic particles.
Finally, the desired Fe3O4/wax composite microspheres were
dispersed in ethyl alcohol.
2.2.3 Synthesis of surface-initiated Fe3O4 nanoparticles (Fe3O4−Br)
Fe3O4/wax composite microspheres dispersed in 5 mL ethanol was
injected into the flask with bromoacetic acid (300 mg) under a dry
nitrogen atmosphere. The mixture was maintained in a light-
resistant container at room temperature for 48 h under mechanical
stirring. Following completion of the reaction, the brown suspension
was first washed with ethyl alcohol to remove the unreacted
bromoacetic acid, then washed with chloroform to dissolve wax, and
separated the final products using magnets. Finally, the Fe3O4-Br
nanoparticles were obtained and dispersed in ethyl alcohol (20
mg/mL 5 mL).
2.2.4 Synthesis of Fe3O4−PMMA Janus nanoparticles via ARGET-
ATRP
In the process of polymerization of PMMA, sodium ascorbate (5.16
mg, 26 μmol) was first placed in a dry round bottomed flask,
vacuumized and infiltrated with nitrogen for three times. To adjust
the length of PMMA, different amount of methyl methacrylate (67
μL, 134 μL, 201 μL, 268 μL which are respectively correspond to
molar ratio of MMA to Fe3O4-Br are 1:25, 1:50, 1:75, 1:100) was
added into the flask. Then Cu2+/PMDETA solution (130 μL, 260 μL,
390 μL, 520 μL ) and aforementioned Fe3O4−Br (20 mg/mL 5 mL) ethyl
alcohol solution were sequentially injected into reaction mixture
(Cu2+/PMDETA solution was obtained by mix 22.235 mg of CuBr2 and
208.8 μL of PMDETA in 5 mL of DMF). The mixture was magnetically
stirred in a light-resistant container at 70 ℃ for 12 h. The brown
suspension was then washed with ethyl alcohol to remove
superfluous methyl methacrylate under an external magnetic field.
Finally, Fe3O4−PMMA Janus nanoparticles were dispersed in ethyl
alcohol.
2.2.5 Synthesis of pyrene-containing Janus Fe3O4 nanoparticles
Fluorescence-polymer were grafted to the end of PMMA grafted on
the Janus Fe3O4 nanoparticles to investigate the self-assembly
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behavior. Pyren-1-ylmethyl methacrylate monomer (PyMMA) (10 mg)
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was individually dissolved in toluene (1 mL).
DOI:The PyMMA solution
10.1039/C6RA04648G
was then injected into the aforementioned Janus Fe3O4
nanoparticles reaction suspension with magnetic stirring for 2 h. The
product was washed several times with ethyl alcohol to remove
redundant monomer under an external magnetic field. Finally, Janus
Fe3O4 nanoparticles with fluorescent groups were dispersed in ethyl
alcohol.
2.2.6 Fluorescent image Experiments
After above-mentioned pyrene-containing Janus Fe3O4 nanoparticles
were synthesized, we characterized their fluorescent features.
Pyrene-containing Janus Fe3O4 nanoparticles ethyl alcohol solution
RSC Advances Accepted Manuscript
(60 μL, 20 mg/mL) was respectively dropped into 4 mL of DMF and
water in a glass vessel. Both vessels were placed in ultraviolet
chamber for treatment at 345 nm and were taken photo.
2.2.6 Emulsification Experiments
To verify whether the Janus Fe3O4 nanoparticles had ability to be
used as emulsifier in two phases, 6 mg of Fe3O4-PMMA50 (the
number behind PMMA denotes the degrees of polymerization of the
polymers) Janus nanoparticles were added into the solution
containing 2 mL of water and 2 mL of toluene. The mixture was then
emulsified in a shaker at 1200 rpm for 50 min at room temperature.
2.3 Measurements and characterization
The morphologies of Fe3O4 nanoparticles, Fe3O4/wax emulsion, and
Janus Fe3O4 nanoparticles in different solvents were imaged using
field-emission scanning electron microscopy (SEM, S-4800, Japan
electronic) at an acceleration voltage of 6 kV. For SEM observation,
samples were prepared on single monocrystal silicon sheet and dried
under ambient conditions. The self-assembly morphologies of the
Janus Fe3O4 nanoparticles in different solvents were further imaged
by transmission electron microscopy (TEM) and atomic force
microscope (AFM). For TEM observation, a drop of the Janus Fe3O4
nanoparticles self-assembly solution was placed on the surface a
copper grid and dried under ambient conditions before viewed on a
field-emission TEM (Tecnai G2F20S-TWIN instrument operating at
120 kV). For AFM measurement, a drop of the Janus Fe3O4
nanoparticles self-assembly solution was placed on a freshly cleaved
mica plate and were dried overnight at room temperature. The
hydrodynamic diameters and size distributions of in water were
measured with dynamic light scattering (DLS, Malvern Nano-ZS, l =
632.8 nm). For DLS measurement, Janus Fe3O4 nanoparticles with a
concentration of 0.6 mg/mL in Milli-Q water was tested at 25 ℃.
The successful conjugation of PMMA brushes on Fe3O4 nanoparticles
were determined by fourier transform infrared spectroscopy (FTIR),
X-ray photoemission spectroscopy (XPS) and thermogravimetric
analysis (TGA). FTIR spectra were collected using fourier transform
infrared (FTIR, Perkin Elmer spectrometer) spectra recorded with
wavenumber range of 500–4000 cm-1. X-ray photoemission
spectroscopy (XPS) was recorded on a Kratos XSAM 800 instrument
equipped with a monochromatic Al anode X-ray gun (12 kV, 15 mA,
10−5Pa). To confirm controllable synthesis of PMMA in ARGET-ATRP,
thermogravimetric analysis (TGA) measurements were performed
with simultaneous thermal analysis (STA 449 C Jupiter, NETZSCH).
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Figure 1. SEM images of the Fe3O4/wax particles fresh (a, b) and one week later (c).
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The mass loss of the dried sample was monitored under N2 at later (Figure 1c). These results suggested that Pickering emulsions

RSC Advances Accepted Manuscript

temperatures ranging from 35 to 800 ℃ with a heating rate of 10 K can be used for the preparation of Fe3O4/wax emulsions. In this
min−1. To obtain magnetization of the Janus Fe3O4 nanoparticles, the process, there were two essential notes. Primarily, the quality ratio
magnetization of the dried sample was measured by a vibrating between Fe3O4 and wax should be regulated appropriately to 1:2 to
sample magnetometer (VSM, Model BHV-525, Riken Japanese insure Fe3O4 nanoparticles homogeneously immobilized on the
Electronics Company) with field from 0 to 20,000 Oe at 300 K. surface of wax sphere. Furthermore, it is should be noted that the
temperature should be lowered to solidify the wax phase to prevent
Self-assembly behaviors of the pyrene-containing Janus Fe3O4
the particles from rotating and wobbling after the formations of
nanoparticles in different solvents were confirmed by Ultraviolet-
emulsion, which is a prerequisite to ensure that only the exposed
Visible spectroscopy (UV-Vis, Lambda 650, Perkin Elmer, USA) at 280
side of each Fe3O4 NPs could be modified in the following procedures.
nm used to study the adsorption of the pyrene aggregate at room
temperature. A Hitachi F-7000 fluorescence spectrometer was used Following the formation of Fe3O4/wax particles, the exposed
to qualitatively monitor the aggregation of pyrene molecules. For hemisphere of Fe3O4 NPs sphere have to be replaced with
Ultraviolet-Visible and fluorescence spectrometer measurement, bromoacetic acid to prepare the Fe3O4-Br NPs via ligand exchange
Janus Fe3O4 nanoparticles with a concentration of 0.6 mg/mL in Milli- reaction. To verify whether Fe3O4/wax particles have been selective
Q water, DMF, and THF were tested at 25 ℃. modified with bromoacetic acid, energy-dispersive X-ray (EDX) was
first used to analysis the relative contents of elements of Fe3O4-Br
3 Results and discussion NPs. As shown in Figure 2b, the relative content of O, C, Fe and Br
In the present study, we proposed a novel strategy that combines has confirmed that bromoacetic acid (as the initiator for ARGET-ATRP)
Pickering emulsions and ARGET-ATRP to synthesize amphiphilic has been successfully grafted to the surface of Fe3O4 NPs via the
Janus Fe3O4 nanoparticles. As shown in Scheme 1, polyol process ligand exchange reaction. To prove that only hemisphere of Fe3O4
prepared Fe3O4 NPs was first combined with molten paraffin wax to NPs sphere has been grafted with bromoacetic acid under wax
prepare the Fe3O4/wax composite microspheres; then the exposed protection, Fe3O4 NPs with all of the surface hydroxyl groups
hydroxyl groups on each Fe3O4 NPs were replaced with bromoacetic
acid to obtain the Fe3O4-Br NPs via the ligand exchange reaction;
following washed with chloroform to remove the wax, ARGET-ATRP
was applied to graft PMMA brushes on hemisphere of Fe3O4-Br NPs
to acquire the amphiphilic Janus Fe3O4 nanoparticles.
It’s well known that nanoparticles (i.e. SiO2) with low absorption
energy are not able to form stable emulsions via the Pickering
emulsions, due to the high surface energy of emulsions that have
high tendency to intergrade.8 While, this embarrassment might be
efficient addressed by the polyol process prepared Fe3O4 NPs which
has excellent dispersibility as well as minimal thermal energy (The
morphologies and structures of as-prepared hydrophilic Fe3O4
nanoparticles are characterized by TEM and XRD, shown in Figure S1,
S2.) that can be stably adsorbed onto the surface of an oil-in-water
emulsions to reduce the total free energy (Figure S3, supporting
information). To validate it, we first observed the morphologies of
Fe3O4/wax composite spheres by SEM. It could be clearly observed Figure 2. Visual evaluation of the Fe3O4 NPs with different
that a homogeneous Fe3O4/wax composite spheres with a mean embellishments. Their colors diversity (a), response to magnetic field
diameters about 15 μm were independently scattered on the wax (c, d), and the EDX spectrum of Fe3O4-Br NPs (b). (Fe3O4-Br and
substrate, and Fe3O4 NPs with a mean diameters about 12 nm were Fe3O4/Br represent Fe3O4 nanoparticle whose superficial hydroxy
evenly distributed on the surface of wax (Figure 1b). Besides, the partially replaced and roundly replaced by bromoacetic aid,
morphology of these emulsions remained a high stationary a week respectively.)

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a)
C-C
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c) d) C=O
O=C-O
Figure 3. XPS of hydroxylated Fe3O4 nanoparticles (a) and Janus Fe3O4 nanoparticles (b). XPS high-resolution scan of carbon
(c), oxygen (d), and iron (e) spectra for hydroxylated Fe3O4 nanoparticles (MNPs) and Janus Fe3O4 nanoparticles (J-NPs).
modified with bromoacetic acid has been synthesized as a control
materials, named as Fe3O4/Br NPs. The colorimetric diversity of Fe3O4
NPs with different embellishments (Fe3O4-Br or Fe3O4/Br) could be
observed intuitively (Figure 2a). With the increase of the
bromoacetic acid substitution degree, the colour of the solution
faded more prominently and response to magnetic field more quickly
(Figure 2c, d). These results demonstrated that only the exposed
hemisphere of the Fe3O4 NPs sphere on wax has been grafted with
bromoacetic acid via the ligand exchange reaction.
It is reported that ARGET-ATRP has been widely utilized for the
synthesis of polymers due to its mild reaction conditions, simple
experimental setup, as well as exquisite controllability. However, it
has rarely been applied to graft the polymer brushes on the inorganic
nanoparticles. Here, to validate whether this useful method could
been used to graft the PMMA brushes on the surface of Fe3O4 NPs,
Fourier transform infrared (FTIR) spectroscopy was first performed.
As shown in Figure S4, in addition to the distinct absorption peak at
590 cm-1 attributed to the Fe-O in both Janus Fe3O4 NPs and pure
Fe3O4 NPs, the presence of a new peak at 1750 cm−1, which is
attributed to the characteristic carbonyl absorption peak for PMMA
(−C(=O)OC−), can suggest the successful conjugation of PMMA
brushes to the surface of Fe3O4 NPs.
Apart from FTIR, X-ray photoelectron spectroscopy (XPS) was
further employed to confirm the conjugation of PMMA brushes to
the surface of Fe3O4 NPs. As shown in Figure 3a and 3b, C, O, and Fe,
were detected both on the Janus Fe3O4 nanoparticles and the
hydroxylated Fe3O4 nanoparticles. To get a better understanding for
the elemental composition of the Janus Fe3O4 nanoparticles (J-NPs)
and the hydroxylated Fe3O4 nanoparticles (MNPs), high-resolution
XPS scans were performed for C, O, and Fe analysis. As shown in
Figure 3c, 3b and 3e, the carbon high resolution scan showed that
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DOI: 10.1039/C6RA04648G
Fe3O4
e)
RSC Advances Accepted Manuscript
the C−H/C−C peak was significantly stronger for the J-NPs than the
MNPs. This is expected from the significantly larger number of C−C
bonds in PMMA. The presence of PMMA on the Janus Fe3O4
nanoparticles was also confirmed by a peak for −(C=O)OC− at 289.9
eV (Figure 3c). The oxygen high resolution scan of J-NPs not only
showed one peak at 530 eV that matched the expected Fe3O4
nanoparticles, but also had a peak at 532 eV for C=O, which proved
the presence of PMMA (Figure 3d). Finally, two peaks for Fe3O4 were
identified at 710.6 and 724.1 eV and assigned to Fe 2p3/2 and Fe
2p1/2, respectively. Due to only half sphere of the Fe3O4
nanoparticles were modified half, magnetic core was not packaged
totally. Accordingly, both of them could be detected identically
(Figure 3e). These results confirmed the presence of PMMA in the
resulting Janus Fe3O4 nanoparticles, which corroborated the FTIR
results. In addition, a layer of corona could be observed clearly on
hemisphere of Janus Fe3O4 nanoparticle sphere from high-resolution
TEM images, which attribute to PMMA. (Figure S5, supporting
information) Combined with results from previous SEM images, EDX
spectrum and FTIR spectrum, we conclude that the combination of
Pickering emulsions approach and AGERT-ATRP method provide a
promising strategy that can be used for the preparation of Janus
Fe3O4 nanoparticles in a gentle, simple and highly controllable
reaction method.
To evaluate the controllability of ARGET-ATRP for the graft of
PMMA brushes to the surface of the Janus Fe3O4 nanoparticles, we
obtained thermal gravimetric analyzer (TGA) curves of different
Janus Fe3O4 nanoparticles (J-NPs25, J-NPs50, and J-NPs100, which
respectively denotes the polymerization degree of PMMA is 25, 50
and 100). As shown in Figure 4a, all Janus Fe3O4 nanoparticles
exhibited evident weight loss, comparing with the hydroxylated
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a) b)
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DOI: 10.1039/C6RA04648G

Figure 4. TGA curves (a) and magnetization curves (b) of

hydroxylated Fe3O4 nanoparticles (MNPs), Janus Fe3O4 nanoparticles
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with different PMMA polymerization degrees (J-NPs25, J-NPs50, J-

RSC Advances Accepted Manuscript

NPs100).

Fe3O4 nanoparticles (MNPs). The weight loss at temperature less

than 200 ℃ was resulted from the evaporation of moisture. While
the weight loss at 200–550 ℃ was attributed to the decomposition
of PMMA brushes as well as the decomposition of triethylene glycol.
Throughout the testing temperature ranges, the weight loss for J-
NPs25, J-NPs50, J-NPs100 and MNPs were 17%, 22%, 32% and 5%,
respectively, indicated that the magnetic content of J-NPs25, J-NPs50,
J-NPs100 and MNPs was 83%, 78%, 68% and 95%, respectively.
Considering the weights of hydroxyl and other impurities, the quality
percentage of grafted PMMA brushes of J-NPs25, J-NPs50, and J-
NPs100 was calculated to be about 12 wt % 17 wt %, and 28 wt %
respectively. Under similar reaction conditions, these three kinds of
J-NPs had similar polymer graft densities if all reaction sites were
available. It proved the controllable conjugation of PMMA brushes
on the Janus Fe3O4 nanoparticles.
In view of the polymer brushes may affect the magnetization of
Fe3O4 nanoparticles, we obtained the magnetization curves of
different Janus Fe3O4 nanoparticles via the vibrating sample
magnetometer. As shown in Figure 4b, neither magnetic remanence
nor coercivity was observed, indicated that both Janus Fe3O4
nanoparticles and MNPs are superparamagnetic. The saturation
magnetization value of J-NPs25, J-NPs50 and J-NPs100 was 53, 52,
and 51 emu/g, respectively, which was slightly lower than that of
MNPs (60 emu/g), yet was better than that in previous reports.17, 31
These results indicated that the magnetic properties of J-NPs
remained excellent and that this moderate synthesis strategy
effectively maintained the superparamagnetism of Janus Fe3O4
nanoparticles.
Figure 5. SEM images (a, b) and TEM images (c, d) of J-NPs100
assemblies, which were respectively self-assembled in water (a, c)
or in DMF (b, d).
like assembly. Besides, these assemblies are prone to agglomerate
due to the entanglement of PMMA brushes. The TEM (Figure 5c and
5d) and AFM (Figure 6) images further demonstrated that these
assemblies have similar shuttle-like structure in water and spherical-
like structure in water.
To better understanding the mechanism for the self-assembly
behaviors of Janus Fe3O4 nanoparticles, hydrophobic fluorescent
pyrene containing polymers were grafted to the end of the PMMA
brushes to intuitively detect the self-assembly behaviors of the Janus
Fe3O4 nanoparticles in different solvents. As shown in Figure 7a, the
characteristic absorption bands of pyrene (330 and 345 nm) was
observed in DMF, however, no absorption peaks were observed in
water. These results demonstrated that when the J-NPs were
dropped into water, the fluorescent hydrophobic P(MMA-b-Py) (Py
a) 300.0 nm
200
100
0
-100
-200

The self-assembly behaviors of Janus Fe3O4 nanoparticles under 0.0 1.0 2.0 3.0 4.0 5.0
different solution conditions were measured by SEM, TEM and AFM.
b)
As shown in Figure 5a, J-NPs100 could quickly self-assembled to form 300.0 nm
a shuttle-like assembly with hydrodynamic diameters ranging from 300

100 to 300 nm. Notably, these assemblies have rough surface, since 150

the hydrophilic hemisphere of the Janus Fe3O4 nanoparticles were 0

arranged outside, and the hydrophobic PMMA brushes were -150
confined inside the assemblies resulting in the overall free energy of -300
the system are minimized.26 However, when self-assembly occurs in
DMF (Figure 5b), the hydrophobic PMMA brushes tend to stretch in 0.0 1.0 2.0 3.0 4.0 5.0
DMF while the hydrophilic hemisphere of Janus Fe3O4 nanoparticles Figure 6. AFM images of J-NPs100 assemblies in water (a) and DMF
were entrapped inside the self-assemblies, presenting a spherical- (b).

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a) b)
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c)
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Self-assembly in water

RSC Advances Accepted Manuscript

Fluorescent amphiphilic
Janus Fe3O4 nanoparticles

Self-assembly in DMF

Figure 7. UV-vis spectra of pyrene-labelled J-NPs100 in DMF and

water (a), fluorescence emission spectra of pyrene-labelled J-NPs100
in DMF, water and THF (λex = 345 nm) (b), schematic illustration for
the self-assembly behaviors of pyrene-labelled J-NPs100 in water or Figure 8. TEM images of different J-NPs assemblies in water: J-NPs25
in DMF, as well as their fluorescent images in different solvents (c). (a) J-NPs50 (b), J-NPs75 (c), and J-NPs100 (d).

represents the pyren-1-ylmethyl methacrylate) brushes would be Fe3O4.34 To verify it, we performed the emulsion experiment. As
densely packed inside the assemblies so the UV absorption peak was shown in Figure 9a, when J-NPs50 were added into the toluene-
difficult to detect. Conversely, in organic solution, fluorescent water model system, emulsions were successfully generated within
hydrophobic P(MMA-b-Py) brushes were exposed outside, and the 50 minutes shaking. It should be noted that J-NPs50 could form large
UV absorption bands of PPy were detected easily and obviously. amount emulsions with low usage (1.25 mg/mL), comparing with
Furthermore, in the fluorescence spectra, the characteristic emission conventional particle emulsifier (12.5 mg/mL) (Figure 9b).11
peak of PPy at 478 nm was observed both in DMF and THF solution
(Figure 7b). In comparison, the emission peak of PPy was relatively
weak in water. Fluorescence imaging (Figure 7c) further confirmed
that Janus Fe3O4 nanoparticles have different self-assembly
behaviors in different solvent.
To investigate the influence of PMMA brushes length on the self-
assembly behaviors of the Janus Fe3O4 nanoparticles, different self-
assemblies were observed via TEM. As shown in Figure 8, the self-
assemblies of J-NPs25, J-NPs50, J-NPs75, and J-NPs100 had a
diameter range of 35 nm, 60 nm, 80 nm, and 150 nm in water,
respectively. With the increase of PMMA brushes, the size of the self-
assemblies became larger, and the morphology became plump. The
hydrodynamic diameter of J-NPs25, J-NPs50, J-NPs75, and J-NPs100
was 35 nm, 60 nm, 80 nm, and 150 nm respectively, as determined
by dynamic light scattering (DLS), which further indicated that the
size and size distribution of the self-assemblies increased with the
increase of PMMA polymerization degree (Figure S6, Supporting
Information).
As demonstrated above, the as-received Janus Fe3O4
nanoparticles exhibited highly controllable self-assembly behaviors
in different solvents and excellent amphipathic structures, which Figure 9. Influence of shaking time (a) on the emulsification in
indicated that they may be highly suitable for use as particulate toluene-water (v/v = 1) system with 1.25 mg/mL J-NPs50; 0 min (A1),
emulsifier since they can be orderly and steadily absorbed onto the 15 min (B1), 30 min (C1), 50 min (D1), and 100 min (E1). Influence of
oil-water interphase because of their superior amphipathy. Besides, standing time (b) on the emulsification toluene-water (v/v = 1)
emulsions based on the Janus Fe3O4 nanoparticles might be easily system with 1.25 mg/mL J-NPs50; 2 days (A2), 4 days (B2), 6 days
separated by a magnet owing to the intrinsic superparamagnetism of (C2), and 8 days (D2).

This journal is © The Royal Society of Chemistry 20xx RSC Advances, 2016, 00, 1-3 | 7

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ARTICLE
Meanwhile, these emulsions were capable of maintaining steady for
a long period (8 days). All Janus Fe3O4 nanoparticles displayed
emulsification effect in tol uene-water model system, however J-
NPs50 played the most important role in emulsification due to its
balance between hydrophilic-hydrophobic domains (Figure S7,
supporting Information).
4 Conclusions
In summary, we firstly proposed a novel strategy to provide a
Published on 31 March 2016. Downloaded by University of California - San Diego on 01/04/2016 07:29:21.
versatile platform that combined the Pickering emulsions
method and ARGET-ATRP approach to synthesize amphiphilic
Janus Fe3O4 nanoparticles. This strategy efficiently conquered
deficiencies lying in conventional synthesis methods for
amphipathic Janus Fe3O4 nanoparticles, such as low saturation
magnetization and poor self-assembly morphology in solvent
etc. The as-received Janus Fe3O4 nanoparticles with a mean
diameter around 12 nm exhibited highly controllable self-
assembly behaviours in different solvents (from shuttle-like
topography to sphere-like topography as well as particle size
range from about 35 nm to 150 nm) and prominent
emulsification in toluene-water model system due to their
excellent amphipathy. More importantly, these emulsions could
not only maintain excellent stability (8 days) even in an
extremely low usage of Janus Fe3O4 nanoparticles as 1.25
mg/mL, but also be easily separated by an external magnet
because of the intrinsic superparamagnetism of Fe3O4. The
results implied that the synthesized Janus Fe3O4 nanoparticles
might have extensive application prospects in oil purification
from oil-water compounds. Moreover, this strategy of
preparation of Janus magnetic materials can also be a guidance
to prepare nano-scale anisotropic materials which reveal each
independently functional modification
Acknowledgements
Financial support was gratefully acknowledged from National
Natural Science Foundation of China (No. 21571134 ，
51273127), International cooperation Program between China
and Germany (No. GZ905), Project in the Science and
Technology Support Program of Sichuan Province (No.
2014GZ0049 and 2015JY0074).
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DOI: 10.1039/C6RA04648G
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RSC Advances Accepted Manuscript

In this paper, we first report a novel strategy that combines Pickering emulsions

approach and ARGET-ATRP method to synthesize amphipathic Janus Fe3O4

nanoparticles. This strategy not only conquers deficiencies lying in conventional

methods such as decrease of saturation magnetization etc. but also exhibits exquisite

control in synthesis of polymer. Consequently, the prepared Janus Fe3O4 nanoparticles

with a mean diameter around 12 nm possess exhibited highly controllable

self-assembly behaviors in different solvents (from shuttle-like topography to

sphere-like topography as well as particle size range from 35 nm to 150 nm). Overall,

these results suggest that the combination of Pickering emulsions and ARGET-ATRP

provide a versatile platform for the preparation of amphipathic Janus Fe3O4

nanoparticles. More importantly, the synthesized amphipathic Janus Fe3O4

nanoparticles have been proved to be a promising emulsifier in toluene-water model

system owing to their minimal usage (1.25 mg/mL) and high stability (emulsification

kept for 8 days), comparing with other particulate emulsifier.