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Synthesis, particle shape characterization and surface modification of

superparamagnetic iron oxide nanochains

Article  in  Materials Characterization · December 2018

DOI: 10.1016/j.matchar.2018.12.014

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 Materials Characterization 148 (2019) 123–133

Contents lists available at ScienceDirect

Materials Characterization
journal homepage: www.elsevier.com/locate/matchar

Synthesis, particle shape characterization, magnetic properties and surface T

modification of superparamagnetic iron oxide nanochains
⁎
Marin Tadica, , Slavko Kraljb, Lazar Kopanjac,d
a
Condensed Matter Physics Laboratory, Vinca Institute, University of Belgrade, Mike Petrovica Alasa 12-14, POB 522, 11001 Belgrade, Serbia
b
Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia
c
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, PO Box 3503, 11120 Belgrade, Serbia
d
Faculty of Mathematics and Computer Science, Alfa BK University, Palmira Toljatija 3, 11070 Belgrade, Serbia

A R T I C LE I N FO A B S T R A C T

Keywords: We report monodisperse, chain-like particles (nanochains) consisted of silica-coated maghemite (γ-Fe2O3) na-
Image analysis noparticle clusters prepared by colloidal chemistry and magnetic field-induced self-assembly of nanoparticle
Shape anisotropy clusters. In order to quantify the shapes of chain-like particles, we have used the measure for shape convexity
Iron oxide which is also called solidity. We functionalize the surface of the nanochains with amino (eNH2) and carboxyl
maghemite
groups (eCOOH) in order to modify surface charge. These surfaces of nanochains provide better colloidal sta-
Synthesis
Superparamagnetism (SPION)
bility and their potential for practical applications in biomedicine. The enhanced colloidal stability of the surface
Chemical surface coating modified nanochains is confirmed by Zeta potential (ζ-potential) analysis. Magnetic properties of the nanochains
show superparamagnetic state at room temperature since the nanochains are composed of tiny nanoparticles as
their building blocks. The measured M(H) data at room temperature have been successfully fitted by the
Langevin function and magnetic moment μp = 20,526 μB for sphere-like nanoparticle clusters and μp = 20,767
μB for nanochains are determined. The determined magnetic parameters have revealed that the nanochains show
a magnetic moment of the nanoparticles higher than the one of individual nanoparticle clusters. These differ-
ences can be attributed to the collective magnetic properties of superparamagnetic iron oxide nanoparticles
(SPION) assembled in different morphologies (isotropic and anisotropic morphology).

1. Introduction
Magnetic nanoparticles can be self-assembled into 1D, 2D and 3D
nanostructures with interesting physical properties that differ with re-
spect to the ones of isolated nanoparticles and bulk counterpart [1–16].
It should be noted that many materials display enhanced physical
properties when they are assembled into a certain structure or mor-
phology. In many applications, such as cell labeling, MRI, hy-
perthermia, sensors, magnetic materials and spintronic, the ordering of
nanoparticles plays the main role [17–20]. Therefore, the significant
challenge in research of nanosized materials are the production of na-
noparticle self-assembly structures with precise size, morphology and
functional control.
Nanostructured iron oxide materials with anisotropic morphology
(1D structures) such as nanotube, nanorod and nanowire are currently
one of the most focused material in science due to their special prop-
erties and potential applications [21–23]. Anisotropic chain-like na-
nostructures (i.e., nanochains) are also one-dimensional materials that
have been much less studied [5,24–26]. Various approaches including
anodic aluminum oxide (AAO) hard template process, dehydroxylation
of lepidocrocite (γ-FeOOH) nanorods and the thermal oxidation of
previously electrodeposited iron nanowires have been developed for
the preparation of one-dimensional magnetic materials [27–34]. The
magnetic shape anisotropy greatly affects on the magnetic properties in
these elongated nanostructures [35–37].
The five polymorphs of iron(III) oxide (α-Fe2O3, β-Fe2O3, γ-Fe2O3,
ε-Fe2O3 and ζ-Fe2O3) and amorphous Fe2O3 have been reported
[38–59]. The most known and studied polymorphs are hematite (α-
Fe2O3) and maghemite (γ-Fe2O3). The maghemite represents one of the
most interesting due to the specific practical applications, such as hy-
perthermia, magnetic resonance imaging, enzyme immunoassay, mag-
netic carriers for drug delivery, information storage, magnetic re-
frigeration, magnetic sensors and ferrofluids [60–67]. It crystallizes in
the cubic crystal system with cation vacancies [68]. Bulk maghemite (γ-
Fe2O3) is a ferrimagnetic material with Curie temperature about
TC = 950 K [68]. However, after decreasing the particle sizes in discrete

⁎
Corresponding author at: Condensed Matter Physics Laboratory, Vinca Institute, P.O. Box 522, 11001 Belgrade, Serbia.
E-mail addresses: marint@vinca.rs (M. Tadic), slavko.kralj@ijs.si (S. Kralj), lazar.kopanja@alfa.edu.rs (L. Kopanja).

https://doi.org/10.1016/j.matchar.2018.12.014
Received 22 August 2018; Received in revised form 24 November 2018; Accepted 12 December 2018
Available online 13 December 2018
1044-5803/ © 2018 Published by Elsevier Inc.
M. Tadic et al.
particles with sizes below 15 nm, γ-Fe2O3 can exhibit super-
paramagnetic properties [50,69–73]. The size and surface effects in-
crease with decreasing γ-Fe2O3 particle size and induced lattice im-
perfection and/or uncompensated magnetic moments at their surface
or/and internal structure [74–77]. The small enough nanoparticles
(below 15 nm) have exhibited interesting properties, such as spin glass,
memory effects, exchange bias, superparamagnetism, etc. [78–80]. In
recent years, one-dimensional chain-like structures of iron oxides have
been reported. Pichon et al. reported formation of anisotropic chain-
like structures of iron oxide nanoparticles with interesting magnetic
properties [81]. They show that large magnetic moments in nano-
particle chains resulted from strong interchain coupling through dipolar
interactions [81]. Wang et al. prepared magnetite nanoclusters and
allowed to self-assemble into 1D nanochains by magnetic field-induced
assembly approach [82]. They have supposed that the transition from
superparamagnetic to ferromagnetic state may be attributed to the
formation of 1D nanochain structure [82]. It has been realized that the
formation of chain-like structures is important for its practical appli-
cations and for fundamental investigations.
Shape descriptors are used in many tasks of a computer vision and
an image processing such as image segmentation, object matching,
classification, recognition and shape identification [83–87]. Convexity
(solidity) is one of the most prominent shape descriptors in the litera-
ture [88–92]. There are various approaches to the definition of solidity
(convexity) [93–97]. In this paper, solidity measure has been defined as
the ratio between the area of nanoparticle with the area of its convex
hull [93].
The tremendous importance of magnetic materials in a wide range
of applications including biomedicine, environmental protection,
magnetoresistance, electromagnetic wave absorption, solar cells, cata-
lysis and lithium-ion batteries have been reported [98–107]. Moreover,
novel synthesis procedures have been recently proposed to synthesize
various nanoparticle structures with high potential for practical appli-
cations [108–120]. In this work our synthesis procedures enables good
control for the formation of the nanochains composed of the nano-
particle clusters. Moreover, advantage of our preparation method is the
possibility to tune the spacing between neighboring nanoparticle clus-
ters inside individual nanochains by controlling the thickness of the
silica shell of the nanoparticle clusters.
In this work, we report the synthesis of uniform nanochains, as well
as quantification of their morphology, functionalization, colloidal sta-
bility and magnetic properties. The nanochain properties are compared
to their primary building blocks composed of spherical self-assembled
maghemite nanoparticle clusters. We have defined the nanoparticle
solidity S(N) by comparing the area of nanoparticle N with the area of
its convex hull. We have used an automated TEM image analysis
method using a MATLAB code for computing solidity measure of chain-
like nanoparticles. The magnetic measurements show super-
paramagnetic properties of the samples and enhanced magnetic mo-
ment of the nanoparticles in nanochain structures compared to its
spherical building blocks.
2. Experimental
2.1. Materials
The chemicals were of reagent grade from commercial sources.
Primary magnetic nanoparticle clusters were kindly provided by Nanos
Scientificae Ltd. (Nanos SCI) under the ‘iNANOvative™|silica cr’ tra-
demark. Tetraethoxysilane (TEOS, 99.9%), 3-(2-aminoethylamino)
propylmethyldimethoxysilane (APMS, 97%), ammonium hydroxide
solution (25% aq.), succinic anhydride (SA, 99%) polyvinylpyrrolidone
(PVP, MW 40 kDa) were purchased from Alfa Aesar. The acetone
(AppliChem GmbH), NH4OH (aq) (Fluka, p.a., 25%), ethanol absolute
(Carlo Erba, reagent–USP) were used as received.
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Materials Characterization 148 (2019) 123–133
2.2. Synthesis of the Nanochains
The syntheses procedures for the silica-coated nanoparticle clusters
as well as for the nanochains have been published elsewhere
[121–124]. These nanoclusters were synthesized by the self-assembly of
primary maghemite nanoparticles followed by coating of the na-
noclusters with a layer of silica. First, single maghemite (γ-Fe2O3) na-
noparticles were synthesized using precipitation from an aqueous so-
lution. In brief, a solution of Fe2+ (0.027 mol L−1) and Fe3+
(0.023 mol L−1) ions was precipitated with concentrated ammonia
(25%) in two steps. In the first step, the pH value of the solution was
raised to pH 3 and maintained at a constant value for 30 min to pre-
cipitate the iron hydroxides. In the second step, the pH value was fur-
ther increased to pH 11.6 to oxidize the iron (II) hydroxide with oxygen
from the air, forming a spinel product. After an aging time of 30 min the
synthesized nanoparticles were thoroughly washed with a diluted am-
monia solution at pH 10.5. The size of the nanoclusters was controlled
by the use of a proper combination of the modified polyacrylic acid
(PAA) and polyvinylpyrrolidone (PVP). PAA is used as a capping agent/
surfactant for the maghemite nanoparticles, whereas the PVP is used as
a promoter for further silica-shell syntheses. The precise control of the
nanocluster size is finally achieved using a high-gradient magnetic se-
parator (HGMS). The description of the silica-coated nanoparticle
cluster synthesis is presented below. For the nanoclusters with thicker
silica shell (~20 nm) an additional silica coating to the commercial 3-
nm-thick silica shell nanoclusters was carried out. 160 mg of the com-
mercial silica-coated nanoclusters with thin silica shell (~3 nm) was
dispersed in 80 ml of ethanol and 2 ml of ammonia. Then, 0.48 ml of
TEOS was added and the reaction mixture was stirred for 6 h. Finally,
the synthesized nanoclusters with a 20-nm-thick silica shell were
magnetically separated from the suspension and washed with EtOH and
then 3-times with distilled water. The description of the nanochains
synthesis is also presented below. First, the aqueous suspension of the
3 nm thick silica-coated clusters was transferred into the polyvinyl
pyrrolidone (PVP, MW 40 kDa) solution at pH 4.3. The sol-gel mixture
was non-magnetically stirred at 250 rpm during the synthesis. A typical
synthesis for the nanochains was carried out at a PVP concentration of
1.25 × 10−4 M, a cluster concentration of 1.6 × 10−8 M, a TEOS con-
centration of 45 mM, exposure to a magnetic field of 65 ± 15 mT for
85 h. The TEOS was added 10 min after the transfer of the clusters into
the PVP solution. The pH value was set to 8.5, by using 0.5% ammonia,
after 80 min of the TEOS addition. The nanochain synthesis with a
~10 nm thick silica shell was completed in 3 h. For the nanochains with
thicker silica shell (~ 40 nm) an additional silica coating was provided.
Therefore, 160 mg of nanochains with thin silica shell (~10 nm) was
dispersed in 80 ml of ethanol and 2 ml of ammonia. Then, 0.8 ml of
TEOS was added and the reaction mixture was stirred for 6 h. Finally,
the synthesized nanochains were magnetically separated from the sus-
pension and washed with EtOH and then 3-times with distilled water.
2.3. Functionalization of the Nanochains
Surface charge of the silica-coated nanochains was modified by
using functionalization with amino- and carboxyl-carrying molecules.
For the amino-functionalized nanochains (nanochains-NH2), the silica-
coated nanochains were grafted by 3-(2-aminoethylamino) pro-
pylmethyldimethoxysilane (APMS), as described elsewhere [125–127].
For the carboxyl-functionalized nanochains (nanochains-COOH), the
nanochains-NH2 were further functionalized with a ring-opening elon-
gation reaction of surface amines with succinic anhydride (SA) in a non-
aqueous medium providing carboxyl functionalization. In brief, 50 mg
of the nanochains-NH2 were dispersed in DMF (35 mL). Then, some SA
(10 mg) dissolved in DMF (15 mL) was slowly added to the suspension,
while being rigorously stirred. The reaction mixture was then stirred
over night at room temperature. After aging, the suspension of the
nanochains-COOH was completely stable. Next, the nanochains-COOH
M. Tadic et al.
were thoroughly washed with ethanol and acetone, and dispersed in
distilled water.
2.4. Sample Characterization
The phase composition of our samples was analyzed by powder X-
ray diffraction by using a Rigaku RINT-TTRIII diffractometer, with Cu-
Kα radiation of λ = 1.5406 A. The structure and morphology of nano-
particles were examined by a JEOL JEM 2100 transmission electron
microscope operating at 200 kV. The suspensions of the functionalized
nanochains were monitored with zeta-potential measurements
(Brookhaven Instruments Corporation, ZetaPALS). For determination of
the zeta-potential of their aqueous suspension as a function of the pH,
prior to the experiment, the aqueous suspension was diluted in an
aqueous solution containing KCl (10 mM). Magnetic measurements
were performed at vibrating-sample magnetometer with the maximum
field of 15 kOe at room temperature (VSM, LakeShore 7400 Series).
3. Results and Discussion
3.1. Structural Characterization (XRD, SAED and TEM)
The structure and phase composition of the sample has been in-
vestigated with the XRD and SAED methods. The XRD and SAED pat-
terns are shown in Fig. 1a and b, respectively. The results in Fig. 1a
reveal that all diffraction peaks are in good agreement with JCPDS file
of maghemite (JCPDS 39-1346) [124]. From the Fig. 1a we can observe
a broad diffraction band centered at about 20 degrees, which corre-
sponds to the amorphous silica matrix. The observed broad peaks in-
dicate that the sample is composed of nanocrystallites. The average
crystallite size of the nanoparticles is about dXRD = 9.8 nm calculated
from the full-width half maximum of the diffraction peak (220) by using
Debye-Scherrer equation (dXRD = Kλ/βcosθ). The selected-area elec-
tron diffraction (Fig. 1b) shows clear diffraction rings characteristic for
nanosized material of spinel structure. We have evaluated the size and
morphology of the particles by transmission electron microscopy
(TEM). Typical TEM images (Fig. 2(a)–(c)) show particles with chain-
like morphology and core-shell structure. The nanoparticle cluster
structure is also clearly seen in Fig. 2(c). The average cross-diameter of
the nanochains is about 80–100 nm, the length is up to 1 μm (average
600 nm) and thickness of the silica shell is either ~10 nm or ~40 nm.
An individual nanoparticle cluster with diameter of ~80 nm is com-
posed of ~90 iron oxide nanocrystals with sizes 8–12 nm which is in
good agreement with XRD analysis.
Fig. 1. (a) The X-ray diffraction pattern of the maghemite nanochains. The Miller indices (hkl) of the diffraction peaks are shown in the pattern. (b) The SAED pattern
of the nanochains.
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Materials Characterization 148 (2019) 123–133
3.2. Morphological Characterization
We have used the measure for shape convexity which is also called
solidity. In order to define solidity measure, it is necessary to explain
the concepts of the convex shape and the convex hull [94]. Planar shape
N will be convex if the line segment drawn between arbitrary points A
and B on the shape always lies inside the shape. The smallest convex set
of points, which contains a shape N is called the convex hull of the
shape N and it is denoted as CH(N).
Definition 1. For a given planar shape N, its solidity (convexity)
measure S(N) is defined in the following way
Area (N )
S (N ) =
Area (CH (N )) (1)
The proposed convexity measure has the following desirable prop-
erties:
a) S(N) is a number from interval (0,1)
b) S(N) = 1 if and only if the measured shape is convex
c) there are shapes whose solidity measure is arbitrary close to 0, i.e.
for each δ > 0 there is a shape N such that 0 < S(N) < δ
d) the solidity measure is invariant with respect to similarity trans-
formations of shape (translation, rotation and scaling),
e) there is a simple and fast procedure for calculating S(N).
f) S(N) is robust with respect to the noise because S(N) depends on the
area of the shape and the area of the convex hull.
In order to illustrate image analysis by using solidity measure S(N),
the shape of two chain-like nanoparticles, which differs in the number
of links (Fig. 3a and c) has been analyzed in this paper. Fig. 3b and d
show the results of the segmentation algorithm, described in [128],
which is applied to the chain-like nanoparticles of Fig. 3a and c, re-
spectively. Figs. 4 and 5 show isolated entire chain-like nanoparticles in
Fig. 3b and d, then their isolated cores and shells. Also, the images of
convex hulls of these shapes are shown. Note that the convex hull of
entire chain-like nanoparticles and convex hull of their shells are
identical. Therefore, convex hulls in Fig. 4b and h are the same, as they
are in Fig. 5b and h. Figs. 4a, d, g and 5a, d, g are used in MATLAB to
calculate the described solidity measure S(N). These values are pre-
sented in Table 1. The values of solidity closer to 1 indicate that the
particle shape is close to the straight convex shape. As it can be seen in
Fig. 3, the nanochain in Fig. 3c has a more compact structure than the
nanochain in Fig. 3a. This notice also shows the numerical values of
M. Tadic et al. Materials Characterization 148 (2019) 123–133

Fig. 2. TEM images of the nanochains.

Fig. 3. (a) and (c) TEM images of chain-like maghemite nanoparticles; (b) and (d) result of segmentation procedure of the images (a) and (c), respectively.

126
M. Tadic et al.
solidity in Table 1. The solidity values are greater for the nanochain in
Fig. 3c in all three cases (entire chain, cores and shell). It can be ex-
plained by the larger contact area between the individual links in the
case of the nanochain in Fig. 3c. Therefore, when it comes to na-
nochains where the links (about the same size and shape) approxi-
mately extend along at the same direction, the solidity measure can be
used to measure the degree of the connectivity of chain links. In the
case of such nanochains (Fig. 3a and c) the solidity value S(N) closer to
1 indicates that the chain links are strongly (firmly) connected, whereas
values closer to 0 indicates a weak connection of the links. It should be
noted that the convex hull of entire chain is identical to the convex hull
of the shell of the same chain, and therefore their areas are equal.
However, the area of the whole chain is much larger than the area of its
shell (hollow structure) and the value of the solidity measure S(N) of
the chain is always much higher than the solidity measure of its shell
(Figs. 4g and 5g). Therefore, the values of S(N) for the shells of the
chains are close to zero, in spite of the strong connections of the links.
The analyses of the nanochains with thicker silica shell (Fig. 6) are also
performed. The determined values of solidity of the nanochains from
Fig. 6 are presented in Table 2. The higher values of the solidity for the
nanochains with thicker silica are observed (Tables 1 and 2).
3.3. Surface Analysis (Zeta Potential) of Silica-Coated Nanochains and
Functionalized with Amino (NH2) and Carboxyl (COOH) Groups
The efficiency of the APMS grafting is followed by using measure-
ments of the zeta-potential of the nanochains in the aqueous suspen-
sions (Fig. 7). The electrophoretic mobility of the nanochains is mea-
sured as the function of the operational pH. The pristine silica shows a
relatively acidic character, because its structure is terminated with
negatively charged –OH surface groups at pH values above the iso-
electric point (IEP) close to pH 3. The zeta-potential curve of the silica-
coated nanochains reaches negative values of around −25 mV at pH
above 7. The high absolute values of the zeta-potential provide strong
electrostatic repulsive forces between the nanochains, providing a good
colloidal stability of the suspension in neutral and basic conditions.
With the grafting of the APMS to the nanochains, the concentration of
surface amino groups decisively defines the nanochains zeta-potential.
The positive surface charge, provided by the surface amino groups,
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Materials Characterization 148 (2019) 123–133
Fig. 4. a) entire isolated chain-like nano-
particle in Fig. 3(b); b) Convex hull of the
shape in Fig. 4(a); c) chain-like nanoparticle
in Fig. 4(a) put in its convex hull in
Fig. 4(b); d) isolated cores of chain-like na-
noparticle in Fig. 3(b); e) Convex hull of the
shape in Fig. 4(d); f) cores of chain-like na-
noparticle in Fig. 4(d) put in its convex hull
in Fig. 4(e); g) isolated shell of chain-like
nanoparticle in Fig. 3(b); h) Convex hull of
the shape in Fig. 4(g); i) shell of chain-like
nanoparticle in Fig. 4(g) put in its convex
hull in Fig. 4(h).
results in the shift of the IEP to pH value of around 8.5. For the carboxyl
functionalization the surface amino groups of the nanochains-NH2 react
with SA. The IEP of the carboxyl-functionalized nanochains (na-
nochains-COOH) in the suspension shifts to a lower pH value (IEP at
pH 4.9) in contrast the original amino-functionalized nanochains. The
negative values of the zeta-potential of around −35 mV at pH above 7.0
ensure good colloidal stability of the suspension in neutral and basic
conditions. The colloidal stability of the nanochains and nanoclusters is
strongly correlated with their zeta potential. Functionalization provides
surface functional groups which effects on the surface charge and
consequently on the zeta potential. It is well recognized that large ab-
solute values (> 30 mV) of zeta potential assure colloidal stability in
carrier liquid. We show that amino and carboxyl functional groups
significantly increase the zeta potential. The high absolute values of the
zeta-potential provide strong electrostatic repulsive forces between the
nanochains, providing a good colloidal stability of the suspension in
neutral and basic conditions.
3.4. Magnetic Characterization (Langevin Model)
The magnetic properties of the anisotropic nanochains and their
spherical (isotropic) counterparts nanoparticle clusters (links of the
nanochains) have been studied by VSM magnetometer. The M(H) de-
pendence of the samples recorded at a temperature of T = 300 K are
shown in Fig. 8. Magnetization curves are typical of superparamagnetic
state (Fig. 8) showing the absence of both coercivity HC = 0 Oe and
remanence Mr = 0 emu/g [129–136]. In case of monodomain magnetic
nanoparticles, the magnetic field H dependence of magnetization M can
be described by the Langevin paramagnetic function [137]:
M = MS L[mp H/kBT] + χH (2)
where L(mpH/kBT) is the Langevin function (L = coth(mpH/kBT)-kBT/
mpH), mp is the magnetic moment per nanoparticle, T is temperature of
the measurements, χ is the high-field magnetic susceptibility (include
any deviations from ideal magnetic order such as disorder and canting
of the sublattices under an applied field) and H denotes the applied
magnetic fields. The fits of Eq. (2) to the M(H) data measured at 300 K
are shown in Fig. 8(a) and (b) (red solid line). The best fit parameters
obtained for nanochains (Fig. 8a) are mp = 20,767 μB and
M. Tadic et al. Materials Characterization 148 (2019) 123–133

Fig. 5. a) entire isolated chain-like nanoparticle in Fig. 3(d); b) Convex hull of the shape in Fig. 5(a); c) chain-like nanoparticle in Fig. 5(a) put in its convex hull in
Fig. 5(b); d) isolated cores of chain-like nanoparticle in Fig. 3(d); e) Convex hull of the shape in Fig. 5(d); f) cores of chain-like nanoparticle in Fig. 5(d) put in its
convex hull from Fig. 5(e); g) isolated shell of chain-like nanoparticle in Fig. 3(d); h) Convex hull of the shape in Fig. 5(g); i) shell of chain-like nanoparticle in
Fig. 5(g) put in its convex hull in Fig. 5(h).

Table 1 χ = 3.297·10−4 emu·g−1 Oe−1. Moreover, the obtained mp of the na-

The value of solidity S(N) for entire chain-like nanoparticles, their cores and nochains is higher than the value obtained in the nanoparticle clusters
shells, i.e. for shapes in Figs. 4a, d, g and 5a, d, g. mp = 20,526 μB (Fig. 8(b)). However, the determined value for high-
Fig. 4a Fig. 4d Fig. 4g Fig. 5a Fig. 5d Fig. 5g field magnetic susceptibility for spherical nanoparticle clusters
χ = 3.646·10−4 emu·g−1 Oe−1 is higher indicating higher contribution
Solidity 0.6878 0.5872 0.1794 0.7789 0.6618 0.2080 of disordered spins. In Fig. 8(c), the magnetization of the nanochains
sample (red squares) and the nanoparticle cluster sample (open circles)
are shown for comparison. It can be seen that the magnetization of

128
M. Tadic et al. Materials Characterization 148 (2019) 123–133

Fig. 6. a) TEM image of chain-like maghemite nanoparticles with thicker silica; b) entire isolated chain-like nanoparticles with convex hulls.

Table 2 shell), NC-40 nm Si (nanochains with 40 nm silica shell), NC-10 nm Si

The value of solidity S(N) for entire chain-like nanoparticles for shapes in (nanochains with 10 nm silica shell), NC-40 nm Si-NH2 (amino-func-
Fig. 6b–f. tionalized nanochains with 40 nm silica shell) and NC-40 nm Si-COOH
Fig. 6b Fig. 6c Fig. 6d Fig. 6e Fig. 6f (carboxyl-functionalized nanochains with 40 nm silica shell) at 300 K
are presented in Fig. 9. It can be seen that the highest magnetization has
Solidity 0.8665 0.9174 0.8975 0.9358 0.9297 nanochain with ~10 nm silica shell. The magnetic measurements
(Fig. 9) show decrease of the saturation magnetization for ~2.5 and
~3.0 emu/g after functionalization with NH2 and COOH groups com-
nanochains increases faster. The higher magnetic moment m of the
pared to pristine silica-coated nanochains, respectively.
maghemite nanoparticles in the anisotropic nanochains also indicates
an enhancement of the collective magnetic properties in anisotropic
chain-like structure. Generally speaking, the magnetic behavior of self- 4. Conclusions
assembled ferrimagnetic nanoparticles is sensitive to the morphology of
the formed structure. Finally, we have found that the difference in the In summary, monodisperse nanochains consisted of maghemite
magnetic properties of the investigated samples is related to the shape nanoparticle clusters have been successfully prepared via colloidal
anisotropy i.e. the morphology of the entire particles. Saturation mag- chemistry and magnetic field-induced self-assembly of nanoparticle
netizations MS of NP-40 nm Si (nanoparticle clusters with 40 nm silica clusters. The results of XRD, SAED, TEM and VSM show that the syn-
thesized sample has a spinel structure, chain-like morphology (diameter

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M. Tadic et al. Materials Characterization 148 (2019) 123–133

of ~80 nm and length of ~600 nm) and superparamagnetic properties

Fig. 7. The curves of the zeta-potentials vs. pH for pristine silica-coated na-
nochains and their amino- and carboxyl- functionalized versions.
at room temperature. In order to quantify the nanochains shape, a so-
lidity (convexity) measure has been used in the case of the nanochains
with different number of links. The solidity is a number from interval
(0,1) where solidity measure of straight (convex-shaped) nanoparticles
is close to 1. It decreases in chain-like nanoparticles. It has been shown
that solidity can be used as a shape descriptor to determine the degree
of connection between the chain links (less solidity values denote a
weaker connection of the links). The solidity measure S(N) can be also
used for estimating the thickness of the shell and magnetization value
i.e., less solidity values indicate a thinner silica shell and higher mag-
netization of the iron oxide nanochains. The good nanochains stability
in water is confirmed by ζ-potential analysis that is important for
practical applications in biomedicine. The magnetic properties of
sphere-like nanoparticle clusters and nanochains have been studied.
The comparison of the samples allows us to study the effect of 1D an-
isotropy on the magnetic properties. Magnetic measurements indicate
that when compared with isotropic nanoparticle clusters (sphere-like
morphology), the assembled chain-like structure displays enhanced
collective magnetic properties, including magnetic moment m, which
are attributed to the collective magnetic properties of the SPIONs. The

Fig. 8. Field-dependent magnetization curves of (a) nanochains and (b) nanoparticle clusters at 300 K. Insets: 1) upper corner: bare nanoparticle cluster; 2) lower
corner: silica-coated nanoparticle cluster. The red solid line fits to the Langevin function. (c) Plot of M/MS vs. H at 300 K for nanochains and nanoparticle clusters.
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

130
M. Tadic et al.
Fig. 9. Saturation magnetization values (MS) for NP-40 nm Si (nanoparticle
clusters with 40 nm silica shell), NC-40 nm Si (nanochains with 40 nm silica
shell), NC-10 nm Si (nanochains with 10 nm silica shell), NC-40 nm Si-NH2
(amino-functionalized nanochains with 40 nm silica shell) and NC-40 nm Si-
COOH (carboxyl-functionalized nanochains with 40 nm silica shell) at 300 K.
determined value for high-field magnetic susceptibility for spherical
nanoparticle clusters is higher than for nanochains indicating better
spin ordering in the nanochain structures. Moreover, the starting na-
noparticle clusters are same in both samples and differences are only in
the morphology indicating that the nanochain structure have enhanced
magnetization. We have shown that the magnetic properties of as-
sembled maghemite nanoparticles depend on the shape of the formed
structure.
Data availability
The experimental procedures required to reproduce these findings
are available in the “Experimental” section.
Acknowledgement
M.T. and L.K. acknowledges financial support from the Ministry of
Education and Science of the Republic of Serbia (Grant no. III 45015
and III 044006), Serbia-Slovakia bilateral project 2017-2018 (SK-SR-
2016-0055) and Serbia-Belarus 2018-2019 (451-03-003036/2017-09/
06). S.K. acknowledges financial support from the Slovenian Research
Agency for research core funding no. (P2-0089) and for the projects
“Nanotheranostics based on magneto-responsive materials” (No. J1-
7302) and “Tunnelling nanotubes for innovative urinary bladder cancer
treatments” (No. J3-7494).
References
[1] V. Malik, A. Pal, O. Pravaz, J. Crassous, Hybrid magnetic iron oxide nanoparticles
with tunable field-directed self-assembly, Nanoscale 9 (2017) 14405–14413.
[2] B. Zeng, L. Yang, W. Zheng, J. Zhu, X. Ma, X. Liu, C. Yuan, Y. Xu, L. Dai, Analysis
of the formation process and performance of magnetic Fe3O4@ Poly (4-vi-
nylpyridine) absorbent prepared by in-situ synthesis, J. Mater. Sci. Technol. 34
(2018) 999–1007.
[3] Y. Tang, Q. Chen, R.C.-A.S. Science, Magnetic field induced controllable self-as-
sembly of maghemite nanocrystals: from 3D arrays to 1D nanochains, Appl. Surf.
Sci. 347 (2015) 202–207.
[4] M. Iacob, D. Sirbu, C. Tugui, G. Stiubianu, Superparamagnetic amorphous iron
oxide nanowires self-assembled into ordered layered structures, RSC Adv. 5 (2015)
62563–62570.
[5] A. Zeleňáková, V. Zeleňák, I. Mat'ko, M. Strečková, P. Hrubovčák, J. Kováč,
Superferromagnetism in chain-like Fe@SiO2 nanoparticle ensembles, J. Appl.
Phys. 116 (2014) 33907.
[6] Z. Qiu, Y. Ma, K. Edström, G.A. Niklasson, T. Edvinsson, Controlled crystal growth
orientation and surface charge effects in self-assembled nickel oxide nanoflakes
and their activity for the oxygen evolution reaction, Int. J. Hydrog. Energy 42
131
Materials Characterization 148 (2019) 123–133
(2017) 28397–28407.
[7] Y. Zhuang, Y. Kong, Q. Liu, B. Shi, Alcohol-assisted self-assembled 3D hierarchical
iron (hydr) oxide nanostructures for water treatment, CrystEngComm 19 (2017)
5926–5933.
[8] R. Edla, A. Tonezzer, M. Orlandi, N. Patel, R. Fernandes, N. Bazzanella, K. Date,
D.C. Kothari, A. Miotello, 3D hierarchical nanostructures of iron oxides coatings
prepared by pulsed laser deposition for photocatalytic water purification, Appl.
Catal. B Environ. 219 (2017) 401–411.
[9] J. Brunner, I.A. Baburin, S. Sturm, K. Kvashnina, A. Rossberg, T. Pietsch, et al.,
Self-assembled magnetite Mesocrystalline films: toward structural evolution from
2D to 3D superlattices, Adv. Mater. Interfaces 4 (2017) 1600431.
[10] Z. Fu, Y. Xiao, A. Feoktystov, V. Pipich, M. Appavou, Y. Su, E. Feng, W. Jin,
T. Bruckel, Field-induced self-assembly of iron oxide nanoparticles investigated
using small-angle neutron scattering, Nanoscale 8 (2016) 18541–18550.
[11] D. Toulemon, Y. Liu, X. Cattoën, C. Leuvrey, S. Bégin-Colin, B.P. Pichon, Enhanced
collective magnetic properties in 2D monolayers of Iron oxide nanoparticles fa-
vored by local order and local 1D shape anisotropy, Langmuir 32 (2016)
1621–1628.
[12] H. Yuan, I.J. Zvonkina, A.M. Al-Enizi, A.A. Elzatahry, J. Pyun, A. Karim, Facile
assembly of aligned magnetic nanoparticle chains in polymer nanocomposite films
by magnetic flow coating, ACS Appl. Mater. Interfaces 9 (2017) 11290–11298.
[13] X. Wang, Y. Liao, D. Zhang, T. Wen, Z. Zhong, A review of Fe3O4 thin films:
synthesis, modification and applications, J. Mater. Sci. Technol. 34 (2018)
1259–1272.
[14] S. Liu, J. Mei, C. Zhang, J. Zhang, R. Shi, Synthesis and magnetic properties of
shuriken-like nickel nanoparticles, J. Mater. Sci.Technol. 34 (2018) 836–841.
[15] X. Xue, K. Liu, E.P. Furlani, Theoretical study of the self-assembly and optical
properties of 1D chains of magnetic–Plasmonic nanoparticles, J. Phys. Chem. C
121 (2017) 9489–9496.
[16] W. Zhang, P.K.J. Wong, D. Zhang, J. Yue, Z. Kou, G. van der Laan, A. Scholl, J.-
G. Zheng, Z. Lu, Y. Zhai, XMCD and XMCD-PEEM studies on magnetic-field-as-
sisted self-assembled 1D Nanochains of spherical ferrite particles, Adv. Funct.
Mater. 27 (2017) 1701265.
[17] C. Martinez-Boubeta, K. Simeonidis, A. Makridis, M. Angelakeris, O. Iglesias,
P. Guardia, A. Cabot, L. Yedra, S. Estrade, F. Peiro, Z. Saghi, Learning from nature
to improve the heat generation of iron-oxide nanoparticles for magnetic hy-
perthermia applications, Sci. Rep. 3 (2013) 1652.
[18] C. Jiang, S. Ng, C. Leung, P.P.-J. of Materials, U, Magnetically assembled iron
oxide nanoparticle coatings and their integration with pseudo-spin-valve thin
films, J. Mater. Chem. C 5 (2017) (2017) 252–263.
[19] S. Chen, J. Zhang, S. Jiang, G. Lin, B. Luo, H. Yao, Y. Lin, C. He, G. Liu, Z. Lin, Self-
assembled superparamagnetic iron oxide nanoclusters for universal cell labeling
and MRI, Nanoscale Res. Lett. 11 (2016) 263.
[20] B. Yuan, L. Cademartiri, Flexible one-dimensional nanostructures: a review, J.
Mater. Sci. 31 (2015) 607–615.
[21] O. Lupan, V. Postica, N. Wolff, O. Polonskyi, V. Duppel, V. Kaidas, E. Lazari,
N. Ababii, F. Faupel, L. Kienle, R. Adelung, Localized synthesis of iron oxide na-
nowires and fabrication of high performance nanosensors based on a single Fe2O3
nanowire, Small 13 (2017) 1602868.
[22] C. Maccato, G. Carraro, D. Peddis, G. Varvaro, D. Barreca, Magnetic properties of ε
iron (III) oxide nanorod arrays functionalized with gold and copper (II) oxide,
Appl. Surf. Sci. 427 (2018) 890–896.
[23] Y. Zhong, H. Fan, L. Chang, H. Shao, J. Wang, J. Zhang, C.-N. Cao, Novel iron
oxide nanotube arrays as high-performance anodes for lithium ion batteries, J.
Power Sources 296 (2015) 255–260.
[24] P. Dhak, M.-K. Kim, J.H. Lee, M. Kim, S.-K. Kim, Linear-chain assemblies of iron
oxide nanoparticles, J. Magn. Magn. Mater. 433 (2017) 47–52.
[25] Q. He, T. Yuan, Y. Wang, A. Guleria, S. Wei, G. Zhang, L. Sun, J. Liu, J. Yu,
D.P. Young, H. Lin, Manipulating the dimensional assembly pattern and crystalline
structures of iron oxide nanostructures with a functional polyolefin, Nanoscale 8
(2016) 1915–1920.
[26] Y. Wang, M. Zhang, X. Liu, Y. Sivalingam, E. Xie, W. Han, Facile one-pot synthesis
of chain-like titanium dioxide nanostructure arrays for efficient ultraviolet sen-
sing, Appl. Surf. Sci. 449 (2018) 239–243.
[27] R. Das, J. Alonso, Z. Nemati Porshokouh, V. Kalappattil, D. Torres, M.-H. Phan,
E. Garaio, J.Á. García, J.L.S. Llamazares, H. Srikanth, Tunable high aspect ratio
iron oxide nanorods for enhanced hyperthermia, J. Phys. Chem. C 120 (2016)
10086–10093.
[28] M.N. Tahir, J. Herzberger, F. Natalio, O. Köhler, R. Branscheid, E. Mugnaioli,
V. Ksenofontov, M. Panthofer, U. Kolb, H. Frey, W. Tremel, Hierachical Ni@Fe2O3
superparticles through epitaxial growth of γ-Fe2O3 nanorods on in situ formed Ni
nanoplates, Nanoscale 8 (2016) 9548–9555.
[29] B. Cortés-Llanos, A. Serrano, A. Muñoz-Noval, E. Urones-Garrote, A. del Campo,
J.F. Marco, et al., Thermal route for the synthesis of maghemite/hematite core/
shell nanowires, J. Phys. Chem. C 121 (2017) 23158–23165.
[30] A. Yousefi, S.A. Seyyed Ebrahimi, A. Seyfoori, H. Mahmoodzadeh Hosseini,
Maghemite Nanorods and Nanospheres: synthesis and comparative physical and
biological properties, Bionanoscience 8 (2018) 95–104.
[31] M. Martín, V. Garcés, J.M. Domínguez-Vera, N. Gálvez, Magnetism in living
magnetically-induced bacteria, RSC Adv. 6 (2016) 95220–95226.
[32] H. Shokrollahi, A review of the magnetic properties, synthesis methods and ap-
plications of maghemite, J. Magn. Magn. Mater. 426 (2017) 74–81.
[33] S.H. Xu, G.T. Fei, H.M. Ouyang, Y. Zhang, P.C. Huo, L. De Zhang, Controllable
fabrication of nickel nanoparticle chains based on electrochemical corrosion, J.
Mater. Chem. C 3 (2015) 2072–2079.
[34] X. Zhu, J. Fan, Y. Zhang, H. Zhu, B. Dai, M. Yan, Y. Ren, Preparation of
M. Tadic et al.
superparamagnetic and flexible γ-Fe2O3 nanowire arrays in an anodic aluminum
oxide template, J. Mater. Sci. 52 (2017) 12717–12723.
[35] S. Sundar, R. Mariappan, K. Min, S. Piraman, Facile biosurfactant assisted bio-
compatible α-Fe2O3 nanorods and nanospheres synthesis, magneto physicochem-
ical characteristics and their enhanced biomolecules sensing ability, RSC Adv. 6
(2016) 77133–77142.
[36] U. Khan, N. Adeela, W. Li, M. Irfan, K. Javed, S. Riaz, X.F. Han, Fabrication,
morphological, structural and magnetic properties of electrodeposited Fe3Pt na-
nowires and nanotubes, J. Magn. Magn. Mater. 424 (2017) 410–415.
[37] D. Peddis, G. Muscas, R. Mathieu, P.A. Kumar, G. Varvaro, G. Singh, I. Orue,
D. Gil-Carton, L. Marcano, A. Muela, M.L. Fdez-Gubieda, Studying nanoparticles'
3D shape by aspect maps: determination of the morphology of bacterial magnetic
nanoparticles, Faraday Discuss. 191 (2016) 177–188.
[38] J. Tuček, L. Machala, S. Ono, A. Namai, M. Yoshikiyo, K. Imoto, et al., Zeta-Fe2O3
a new stable polymorph in iron(III) oxide family, Sci. Rep. 5 (2015) 15091.
[39] J. López-Sánchez, A. Muñoz-Noval, A. Serrano, M. Abuín, J. de la Figuera,
J.F. Marco, et al., Growth, structure and magnetism of ε-Fe2O3 in nanoparticle
form, RSC Adv. 6 (2016) 46380–46387.
[40] D.A. Balaev, A.A. Dubrovskiy, K.A. Shaykhutdinov, O.A. Bayukov, S.S. Yakushkin,
G.A. Bukhtiyarova, et al., Surface effects and magnetic ordering in few-nanometer-
sized ε-Fe2O3 particles, J. Appl. Phys. 114 (2013) 163911.
[41] G.A. Bukhtiyarova, M.A. Shuvaeva, O.A. Bayukov, S.S. Yakushkin,
O.N. Martyanov, Facile synthesis of nanosized ε-Fe2O3 particles on the silica
support, J. Nanopart. Res. 13 (2011) 5527–5534.
[42] J.L. García-Muñoz, A. Romaguera, F. Fauth, J. Nogués, M. Gich, Unveiling a new
high-temperature ordered magnetic phase in ε-Fe2O3, Chem. Mater. 29 (2017)
9705–9713.
[43] I. Shanenkov, A. Sivkov, A. Ivashutenko, Influence of oxygen concentration on
plasma dynamic synthesis product in Fe-O system, Solid State Phenom. 265 (2017)
652–656.
[44] S.S. Yakushkin, D.A. Balaev, A.A. Dubrovskiy, S.V. Semenov, K.A. Shaikhutdinov,
M.A. Kazakova, et al., Evolution of the Fe3+ ion local environment during the
phase transition ε-Fe2O3→α-Fe2O3, J. Supercond. Nov. Magn. (2017) 1–9.
[45] A. Sivkov, E. Naiden, A. Ivashutenko, I. Shanenkov, Plasma dynamic synthesis and
obtaining ultrafine powders of iron oxides with high content of ε-Fe2O3, J. Magn.
Magn. Mater. 405 (2016) 158–168.
[46] J. López-Sánchez, A. Muñoz-Noval, C. Castellano, A. Serrano, A. del Campo,
M. Cabero, et al., Origin of the magnetic transition at 100 K in ε-Fe2O3 nano-
particles studied by X-ray absorption fine structure spectroscopy, J. Phys.
Condens. Matter 29 (2017) 485701.
[47] M. Tadic, I. Milosevic, S. Kralj, M. Mitric, D. Makovec, M.-L. Saboungi, et al.,
Synthesis of metastable hard-magnetic ε-Fe2O3 nanoparticles from silica-coated
akaganeite nanorods, Nanoscale 9 (2017) 10579–10584.
[48] J. López-Sánchez, A. Serrano, A. Del Campo, M. Abuín, O. Rodríguez de la Fuente,
N. Carmona, Sol–gel synthesis and micro-Raman characterization of ε-Fe2O3
micro- and nanoparticles, Chem. Mater. 28 (2016) 511–518.
[49] A. Bahiraei, A. Afkhami, T. Madrakian, R. Gheitaran, Preparation and character-
ization of γ-Fe2O3 nanoparticles and investigation of its adsorption performance
for sulfide, sulfite and thiosulfate from aqueous solutions using ultrasonic assisted
method: modeling and optimization, Ultrason. Sonochem. 40 (2018) 1049–1058.
[50] S. Rajput, L.P. Singh, C.U. Pittman, D. Mohan, Lead (Pb2+) and copper (Cu2+)
remediation from water using superparamagnetic maghemite (γ-Fe2O3) nano-
particles synthesized by flame spray pyrolysis (FSP), J. Colloid Interface Sci. 492
(2017) 176–190.
[51] Q. Meng, K. Wang, Y. Tang, K. Zhao, G. Zhang, L. Zhao, One-pot synthesis of Fe2O3
loaded SiO2 hollow particles as effective visible light photo-Fenton catalyst, J.
Alloys Compd. 722 (2017) 8–16.
[52] M. Saad, H. Tahir, Synthesis of carbon loaded γ-Fe2O3 nanocomposite and their
applicability for the selective removal of binary mixture of dyes by ultrasonic
adsorption based on response surface methodology, Ultrason. Sonochem. 36
(2017) 393–408.
[53] A. Bahari, Characteristics of Fe3O4, α-Fe2O3, and γ-Fe2O3 nanoparticles as suitable
candidates in the field of nanomedicine, J. Supercond. Nov. Magn. 30 (2017)
2165–2174.
[54] J. Lee, S.-Y. Kwak, Tubular superstructures composed of α-Fe2O3 nanoparticles
from pyrolysis of metal–organic frameworks in a confined space: effect on mor-
phology, particle size, and magnetic properties, Cryst. Growth Des. 17 (2017)
4496–4500.
[55] N. Jaafarzadeh, F. Ghanbari, M. Ahmadi, Catalytic degradation of 2,4-di-
chlorophenoxyacetic acid (2,4-D) by nano-Fe2O3 activated peroxymonosulfate:
influential factors and mechanism determination, Chemosphere 169 (2017)
568–576.
[56] A.N. Vasiliev, L.V. Shvanskaya, O.S. Volkova, A.V. Koshelev, E.A. Zvereva,
G.V. Raganyan, I.A. Presniakov, A.V. Sobolev, A.M. Abakumov, Y.M. Lvov,
Magnetism of natural composite of halloysite clay nanotubes Al2Si2O5 (OH) 4 and
amorphous hematite Fe2O3, Mater. Charact. 129 (2017) 179–185.
[57] H. Mansour, H. Letifi, R. Bargougui, S. De Almeida-Didry, B. Negulescu, C. Autret-
Lambert, et al., Structural, optical, magnetic and electrical properties of hematite
(α-Fe2O3) nanoparticles synthesized by two methods: polyol and precipitation,
Appl. Phys. A 123 (2017) 787.
[58] J.R. Jesus, R.J.S. Lima, K.O. Moura, J.G.S. Duque, C.T. Meneses, Anisotropic
growth of α-Fe2O3 nanostructures, Ceram. Int. 44 (2018) 3585–3589.
[59] X. Chen, J. Wei, X. Wang, P. Wang, Nanocasting synthesis, magnetic interaction
and gas-sensing properties of dispersed, bundled and assembled α-Fe2O3 nano-
wires, J. Alloys Compd. 705 (2017) 138–145.
[60] D. Baratella, M. Magro, P. Jakubec, E. Bonaiuto, J. de Almeida Roger, E. Gerotto,
132
Materials Characterization 148 (2019) 123–133
et al., Electrostatically stabilized hybrids of carbon and maghemite nanoparticles:
electrochemical study and application, Phys. Chem. Chem. Phys. 19 (2017)
11668–11677.
[61] F. Hasanpour, M. Taei, S.H. Banitaba, M. Heidari, Template synthesis of maghe-
mite nanoparticle in carboxymethyl cellulose and its application for electro-
chemical cabergoline sensing, Mater. Sci. Eng. C. 76 (2017) 88–93.
[62] S. Richard, V. Eder, G. Caputo, C. Journé, P. Ou, J. Bolley, et al., USPIO size
control through microwave nonaqueous sol-gel method for neoangiogenesis T2
MRI contrast agent, Nanomedicine 21 (2016) 2769–2779.
[63] H. Jahangirian, E.G. Lemraski, T.J. Webster, R. Rafiee-Moghaddam, Y. Abdollahi,
A review of drug delivery systems based on nanotechnology and green chemistry:
green nanomedicine, Int. J. Nanomedicine 12 (2017) 2957–2978.
[64] B.A. Otieno, C.E. Krause, J.F. Rusling, Bioconjugation of antibodies and enzyme
labels onto magnetic beads, Methods Enzymol. 571 (2016) 135–150.
[65] S. Richard, M. Boucher, Y. Lalatonne, S. Mériaux, L. Motte, Iron oxide nanoparticle
surface decorated with cRGD peptides for magnetic resonance imaging of brain
tumors, Biochim. Biophys. Acta, Gen. Subj. 1861 (2017) 1515–1520.
[66] A. Farzin, M. Fathi, R. Emadi, Multifunctional magnetic nanostructured hard-
ystonite scaffold for hyperthermia, drug delivery and tissue engineering applica-
tions, Mater. Sci. Eng. C. 70 (2017) 21–31.
[67] C. Guibert, J. Fresnais, V. Peyre, V. Dupuis, Magnetic fluid hyperthermia probed
by both calorimetric and dynamic hysteresis measurements, J. Magn. Magn.
Mater. 421 (2017) 384–392.
[68] R. Grau-Crespo, A.Y. Al-Baitai, I. Saadoune, N.H. De Leeuw, Vacancy ordering and
electronic structure of γ-Fe2O3 (maghemite): a theoretical investigation, J. Phys.
Condens. Matter. 22 (2010) 255401.
[69] P.P. Waifalkar, S.B. Parit, A.D. Chougale, S.C. Sahoo, P.S. Patil, P.B. Patil,
Immobilization of invertase on chitosan coated γ-Fe2O3 magnetic nanoparticles to
facilitate magnetic separation, J. Colloid Interface Sci. 482 (2016) 159–164.
[70] R. Zulfiqar, M.U. Khan, Z. Iqbal Rahman, Variation of structural, dielectric and
magnetic properties of PVP coated γ-Fe2O3 nanoparticles, J. Mater. Sci. Mater.
Electron. 27 (2016) 12490–12498.
[71] G.G. Nedelcu, A. Nastro, L. Filippelli, M. Cazacu, M. Iacob, C.O. Rossi, et al.,
Structural characterization of copolymer embedded magnetic nanoparticles, Appl.
Surf. Sci. 352 (2015) 109–116.
[72] M. Stier, A. Neumann, A. Philippi-Kobs, H.P. Oepen, M. Thorwart, Implications of
a temperature-dependent magnetic anisotropy for superparamagnetic switching,
J. Magn. Magn. Mater. 447 (2018) 96–100.
[73] A. Saravanan, R.P. Ramasamy, Investigation of polymer dynamics in chitosan-
maghemite nanocomposites: a potential green superparamagnetic material, J.
Polym. Res. 23 (2016) 104.
[74] M. Kopáni, J. Hlinková, H. Ehrlich, D. Valigura, Magnetic properties of iron oxides
in the human globus pallidus, J. Bioanal. Biomed. 9 (2017) 080–090.
[75] I. Bezverkhyy, E. Popova, N. Geoffroy, F. Herbst, J.-P. Bellat, Preparation of
magnetic composites of MIL-53(Fe) or MIL-100(Fe) via partial transformation of
their framework into γ-Fe2O3, J. Mater. Chem. A 4 (2016) 8141–8148.
[76] E. Tronc, A. Ezzir, R. Cherkaoui, C. Chanéac, M. Noguès, H. Kachkachi, et al.,
Surface-related properties of γ-Fe2O3 nanoparticles, J. Magn. Magn. Mater. 221
(2000) 63–79.
[77] M.P. Morales, S. Veintemillas-Verdaguer, A.M.I. Montero, C.J. Serna, A. Roig,
L.L. Casas, et al., Surface and internal spin canting in γ-Fe2O3 nanoparticles, Chem.
Mater. 11 (1999) 3058–3064.
[78] J.A. Ramos Guivar, E.A. Sanches, F. Bruns, E. Sadrollahi, M.A. Morales,
E.O. López, et al., Vacancy ordered γ-Fe2O3 nanoparticles functionalized with
nanohydroxyapatite: XRD, FTIR, TEM, XPS and Mössbauer studies, Appl. Surf. Sci.
389 (2016) 721–734.
[79] T.N. Shendruk, R.D. Desautels, B.W. Southern, J. van Lierop, The effect of surface
spin disorder on the magnetism of γ-Fe2O3 nanoparticle dispersions,
Nanotechnology 18 (2007) 455704.
[80] H. Khurshid, P. Lampen-Kelley, Ò. Iglesias, J. Alonso, M.-H. Phan, C.-J. Sun, et al.,
Spin-glass-like freezing of inner and outer surface layers in hollow γ-Fe2O3 na-
noparticles, Sci. Rep. 5 (2015) 15054.
[81] D. Toulemon, M.V. Rastei, D. Schmool, J.S. Garitaonandia, L. Lezama, X. Cattoën,
et al., Enhanced collective magnetic properties induced by the controlled assembly
of Iron oxide nanoparticles in chains, Adv. Funct. Mater. 26 (2016) 2454–2462.
[82] H. Wang, Q.-W. Chen, L.-X. Sun, H. Qi, X. Yang, S. Zhou, et al., Magnetic-field-
induced formation of one-dimensional magnetite nanochains, Langmuir 25 (2009)
7135–7139.
[83] R. Sparks, A. Madabhushi, Explicit shape descriptors: novel morphologic features
for histopathology classification, Med. Image Anal. 17 (2013) 997–1009.
[84] M.A. Aktaş, J. Žunić, A family of shape ellipticity measures for galaxy classifica-
tion, SIAM J. Imag. Sci. 6 (2013) 765–781.
[85] S. Belongie, J. Malik, J. Puzicha, Shape matching and object recognition using
shape contexts, IEEE Trans. Pattern Anal. Mach. Intell. 24 (2002) 509–522.
[86] D. Žunić, J. Žunić, Shape ellipticity from Hu moment invariants, Appl. Math.
Comput. 226 (2014) 406–414.
[87] M.B.H. Rhouma, J. Zunic, M.C. Younis Younis, Moment invariants for multi-
component shapes with applications to leaf classification, Comput. Electron. Agric.
142 (2017) 326–337.
[88] S. Najafian, B. Beigzadeh, M. Riahi, F. Khadir Chamazkoti, M. Pouramir, Fourier-
based quantification of renal glomeruli size using Hough transform and shape
descriptors, Comput. Methods Prog. Biomed. 151 (2017) 179–192.
[89] M. Wiwart, E. Suchowilska, W. Lajszner, Ł. Graban, Identification of hybrids of
spelt and wheat and their parental forms using shape and color descriptors,
Comput. Electron. Agric. 83 (2012) 68–76.
[90] P.L. Rosin, C.L. Mumford, A symmetric convexity measure, Comput. Vis. Image
M. Tadic et al.
Underst. 103 (2006) 101–111.
[91] E. Rahtu, M. Salo, J. Heikkila, A new convexity measure based on a probabilistic
interpretation of images, IEEE Trans. Pattern Anal. Mach. Intell. 28 (2006)
1501–1512.
[92] R. Klette, J. Žunić, ADR shape descriptor – distance between shape centroids
versus shape diameter, Comput. Vis. Image Underst. 116 (2012) 690–697.
[93] S. Yoon, B. Lee, J. Yun, J.G. Han, J.-S. Lee, J.H. Lee, Systematic study of inter-
dependent relationship on gold nanorod synthesis assisted by electron microscopy
image analysis, Nanoscale 9 (2017) 7114–7123.
[94] J. Zunic, P.L. Rosin, A new convexity measure for polygons, IEEE Trans. Pattern
Anal. Mach. Intell. 26 (2004) 923–934.
[95] J. Zunic, P.L. Rosin, A convexity measurement for polygons, IEEE Trans. Pattern
Anal. Mach. Intell. 26 (2002) 173–182.
[96] P.L. Rosin, J. Žunić, Probabilistic convexity measure, IET Image Process. 1 (2007)
182–188.
[97] J. Žunić, P.L. Rosin, Convexity measure for shapes with partially extracted
boundaries, Electron. Lett. 43 (2007) 380–382.
[98] Y. Li, J. Tao, X. Gaofeng, J. Tian, M. Dong, Q. Shao, B. Wang, et al., 3-D magnetic
graphene oxide-magnetite poly (vinyl alcohol) nanocomposite substrates for im-
mobilizing enzyme, Polymer 149 (2018) 13–22.
[99] H. Gu, H. Zhang, J. Lin, Q. Shao, D.P. Young, L. Sun, T.D. Shen, Z. Guo, Large
negative giant magnetoresistance at room temperature and electrical transport in
cobalt ferrite-polyaniline nanocomposites, Polymer 143 (2018) 324–330.
[100] K. Gong, Q. Hu, L. Yao, M. Li, D. Sun, Q. Shao, B. Qiu, Z. Guo, Ultrasonic pre-
treated sludge derived stable magnetic active carbon for Cr (VI) removal from
wastewater, ACS Sustain. Chem. Eng. 6 (2018) 7283–7291.
[101] J. Huang, Y. Cao, Q. Shao, X. Peng, Z. Guo, Magnetic nanocarbon adsorbents with
enhanced hexavalent chromium removal: morphology dependence of fibrillar vs
particulate structures, Ind. Eng. Chem. Res. 56 (2017) 10689–10701.
[102] N. Wu, C. Liu, D. Xu, J. Liu, W. Liu, Q. Shao, Z. Guo, Enhanced electromagnetic
wave absorption of three-dimensional porous Fe3O4/C composite flowers, ACS
Sustain. Chem. Eng. 6 (2018) 12471–12480.
[103] Z. Guo, P. Xie, F. Dang, B. He, J. Lin, R. Fan, C. Hou, H. Liu, J. Zhang, Y. Ma, Bio-
gel derived nickel/carbon nanocomposites with enhanced microwave absorption,
J. Mater. Chem. C 6 (2018) 8812–8822.
[104] J. Huang, Y. Li, Y. Cao, F. Peng, Y. Cao, Q. Shao, H. Liu, Z. Guo, Hexavalent
chromium removal over magnetic carbon nanoadsorbent: synergistic effect of
fluorine and nitrogen co-doping, J. Mater. Chem. A 6 (2018) 13062–13074.
[105] Q. Luo, H. Chen, Y. Lin, H. Du, Q. Hou, F. Hao, N. Wang, Z. Guo, J. Huang, Discrete
iron (III) oxide nanoislands for efficient and photostable perovskite solar cells,
Adv. Funct. Mater. 27 (2017) 1702090.
[106] P. Zhou, S. Wang, C. Tao, X. Guo, L. Hao, Q. Shao, L. Liu, et al., PAA/alumina
composites prepared with different molecular weight polymers and utilized as
support for nickel-based catalyst, Adv. Polym. Technol. 37 (2017) 2325–2335.
[107] H.Y. Du, Y.L. An, Y.H. Wei, L.F. Hou, B.S. Liu, H. Liu, Y. Ma, et al., Nickel powders
modified nanocoating strengthened Iron plates by surface mechanical attrition
alloy and heat treatment, Sci. Adv. Mater. 10 (2018) 1063–1072.
[108] Y. He, S. Yang, H. Liu, Q. Shao, Q. Chen, C. Lu, Y. Jiang, C. Liu, Z. Guo, Reinforced
carbon fiber laminates with oriented carbon nanotube epoxy nanocomposites:
magnetic field assisted alignment and cryogenic temperature mechanical proper-
ties, J. Colloid Interface Sci. 517 (2018) 40–51.
[109] X. Lou, C. Lin, Q. Luo, J. Zhao, B. Wang, J. Li, Q. Shao, X. Guo, N. Wang, Z. Guo,
Crystal structure modification enhanced FeNb11O29 anodes for lithium-ion bat-
teries, ChemElectroChem 4 (2017) 3171–3180.
[110] Q. Luo, H. Chen, Y. Lin, H. Du, Q. Hou, F. Hao, N. Wang, Z. Guo, J. Huang, Discrete
iron (III) oxide nanoislands for efficient and photostable perovskite solar cells,
Adv. Funct. Mater. 27 (2017) 1702090.
[111] T. Liu, K. Yu, L. Gao, H. Chen, N. Wang, L. Hao, T. Li, H. He, Z. Guo, A graphene
quantum dot decorated SrRuO3 mesoporous film as an efficient counter electrode
for high-performance dye-sensitized solar cells, J. Mater. Chem. A 5 (2017)
17848–17855.
[112] P. Xie, Z. Wang, Z. Zhang, R. Fan, C. Cheng, H. Liu, Y. Liu, et al., Silica micro-
sphere templated self-assembly of a three-dimensional carbon network with stable
radio-frequency negative permittivity and low dielectric loss, J. Mater. Chem. C 6
(2018) 5239–5249.
[113] W. Deng, T. Kang, H. Liu, J. Zhang, N. Wang, N. Lu, Y. Ma, A. Umar, Z. Guo,
Potassium hydroxide activated and nitrogen doped graphene with enhanced su-
percapacitive behavior, Sci. Adv. Mater. 10 (2018) 937–949.
[114] Z. Yang, X. Hao, S. Chen, Z. Ma, W. Wang, C. Wang, L. Yue, et al., Long-term
antibacterial stable reduced graphene oxide nanocomposites loaded with cuprous
133
View publication stats
Materials Characterization 148 (2019) 123–133
oxide nanoparticles, J. Colloid Interface Sci. 533 (2019) 13–23.
[115] N. Wu, C. Liu, D. Xu, J. Liu, W. Liu, Q. Shao, Z. Guo, Enhanced electromagnetic
wave absorption of three-dimensional porous Fe3O4/C composite flowers, ACS
Sustain. Chem. Eng. 6 (2018) 12471–12480.
[116] Y. Zheng, Y. Zheng, Z. Wang, Y. Cao, Q. Shao, Z. Guo, Sodium dodecyl benzene
sulfonate-catalyzed reaction for aromatic aldehydes with 1-phenyl-3-methyl-5-
pyrazolone in aqueous media, Green Chem. Lett. Rev. 11 (2018) 217–223.
[117] Y. Zheng, Y. Zheng, S. Yang, Z. Guo, T. Zhang, H. Song, Q. Shao, Esterification
synthesis of ethyl oleate catalyzed by Brønsted acid–surfactant-combined ionic
liquid, Green Chem. Lett. Rev. 10 (2017) 202–209.
[118] C. Lin, L. Hu, C. Cheng, K. Sun, X. Guo, Q. Shao, J. Li, N. Wang, Z. Guo, Nano-
TiNb2O7/carbon nanotubes composite anode for enhanced lithium-ion storage,
Electrochim. Acta 260 (2018) 65–72.
[119] Y. Zhang, L. Qian, W. Zhao, X. Li, X. Huang, X. Mai, Z. Wang, Q. Shao, X. Yan,
Z. Guo, Highly efficient Fe-NC nanoparticles modified porous graphene composites
for oxygen reduction reaction, J. Electrochem. Soc. 165 (2018) H510–H516.
[120] Z. Sun, L. Zhang, F. Dang, Y. Liu, Z. Fei, Q. Shao, H. Lin, et al., Experimental and
simulation-based understanding of morphology controlled barium titanate nano-
particles under co-adsorption of surfactants, CrystEngComm 19 (2017)
3288–3298.
[121] I. Kavre, G. Kostevc, S. Kralj, A. Vilfan, D. Babič, Fabrication of magneto-re-
sponsive microgears based on magnetic nanoparticle embedded PDMS, RSC Adv. 4
(2014) 38316–38322.
[122] S. Kralj, D. Makovec, Magnetic assembly of superparamagnetic Iron oxide nano-
particle clusters into nanochains and nanobundles, ACS Nano 9 (2015)
9700–9707.
[123] S. Kralj, D. Makovec, The chemically directed assembly of nanoparticle clusters
from superparamagnetic iron-oxide nanoparticles, RSC Adv. 4 (2014) 13167.
[124] M. Tadic, S. Kralj, M. Jagodic, D. Hanzel, D. Makovec, Magnetic properties of
novel superparamagnetic iron oxide nanoclusters and their peculiarity under an-
nealing treatment, Appl. Surf. Sci. 322 (2014) 255–264.
[125] S. Kralj, M. Rojnik, J. Kos, D. Makovec, Targeting EGFR-overexpressed A431 cells
with EGF-labeled silica-coated magnetic nanoparticles, J. Nanopart. Res. 15
(2013) 1666.
[126] S. Kralj, M. Rojnik, R. Romih, M. Jagodič, J. Kos, D. Makovec, Effect of surface
charge on the cellular uptake of fluorescent magnetic nanoparticles, J. Nanopart.
Res. 14 (2012) 1151.
[127] S. Kralj, M. Drofenik, D. Makovec, Controlled surface functionalization of silica-
coated magnetic nanoparticles with terminal amino and carboxyl groups, J.
Nanopart. Res. 13 (2011) 2829–2841.
[128] L. Kopanja, S. Kralj, D. Zunic, B. Loncar, M. Tadic, Core–shell superparamagnetic
iron oxide nanoparticle (SPION) clusters: TEM micrograph analysis, particle de-
sign and shape analysis, Ceram. Int. 42 (2016) 10976–10984.
[129] A.B. Salunkhe, V.M. Khot, J.M. Ruso, S.I. Patil, Water dispersible super-
paramagnetic cobalt iron oxide nanoparticles for magnetic fluid hyperthermia, J.
Magn. Magn. Mater. 419 (2016) 533–542.
[130] G. Wang, D. Zhao, Y. Ma, Z. Zhang, H. Che, J. Mu, et al., Synthesis and char-
acterization of polymer-coated manganese ferrite nanoparticles as controlled drug
delivery, Appl. Surf. Sci. 428 (2018) 258–263.
[131] A. Kumar Das, R. Govindaraj, A. Srinivasan, Structural and magnetic properties of
sol-gel derived CaFe2O4 nanoparticles, J. Magn. Magn. Mater. 451 (2018)
526–531.
[132] O. Koshy, M.A. Khadar, Superparamagnetism in undoped ZnO nanorods, Appl.
Surf. Sci. 346 (2015) 528–533.
[133] S. Lin, L. Liu, Y. Yang, K. Lin, Study on preferential adsorption of cationic-style
heavy metals using amine-functionalized magnetic iron oxide nanoparticles
(MIONPs-NH2) as efficient adsorbents, Appl. Surf. Sci. 407 (2017) 29–35.
[134] S. Lin, Y. Yang, G. Chen, X. Chen, W. Zhang, M. Xu, et al., Study on the influence of
thiolation on the adsorption and magnetic recovery of superparamagnetic na-
noadsorbents for Cd2+ removal, Appl. Surf. Sci. 425 (2017) 141–147.
[135] G. Wang, Y. Ma, J. Mu, Z. Zhang, X. Zhang, L. Zhang, et al., Monodisperse poly-
vinylpyrrolidone-coated CoFe2O4 nanoparticles: synthesis, characterization and
cytotoxicity study, Appl. Surf. Sci. 365 (2016) 114–119.
[136] D. Sardar, M. Sengupta, A. Bordoloi, M.A. Ahmed, S.K. Neogi, S. Bandyopadhyay,
et al., Multiple functionalities of Ni nanoparticles embedded in carboxymethyl
guar gum polymer: catalytic activity and superparamagnetism, Appl. Surf. Sci. 405
(2017) 231–239.
[137] M. Tadić, D. Marković, V. Spasojević, V. Kusigerski, M. Remškar, J. Pirnat, et al.,
Synthesis and magnetic properties of concentrated α-Fe2O3 nanoparticles in a si-
lica matrix, J. Alloys Compd. 441 (2007) 291–296.