Journal of Magnetism and Magnetic Materials 519 (2021) 167451

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Journal of Magnetism and Magnetic Materials

journal homepage: www.elsevier.com/locate/jmmm

About the influence of the colloidal magnetic nanoparticles coating on the T

specific loss power in magnetic hyperthermia
Mihaela Osacia, , Matteo Cacciolab
⁎

a
“Politehnica” University of Timişoara, Department of Electrical Engineering and Industrial Informatics, 2 Victoriei Square, 300006 Timişoara, Timiş County, Romania
b
Cooperativa TEC, 439 Via Nazionale, I-89134 Pellaro di Reggio Calabria, Italy

ARTICLE INFO ABSTRACT

Keywords: The current magnetic hyperthermia with nanoparticles is a method of destroying cancer cells, increasingly
Colloid studied theoretically and experimentally. The colloidal magnetic nanoparticle systems used in this method have
Magnetic hyperthermia a pronounced agglomeration tendency that leads to the blocking of blood vessels in the case of intravenous
Nanoparticles coating administration of the nanoparticles. For nanoparticle dispersion stability and biocompatibility, the particles are
Specific loss power
covered with an organic layer. The influence of nanoparticle coating on the generation of heat by magnetic
Langevin dynamics
hyperthermia is very little studied. In this paper, we theoretically study, by numerical simulation, the way in
which the nanoparticle coating affects the agglomeration tendency of the nanoparticles, as well as the specific
loss power which characterises the nanoparticle performance in the generation of heat by magnetic hy-
perthermia. For this purpose, we propose a theoretical model. The self-organisation of colloidal nanoparticles
will be simulated using a Langevin dynamics stochastic method based on an effective Verlet-type algorithm, then
the magnetic relaxation time used in the specific loss power (SLP) relation, obtained based on the theory of
magnetic fluid losses from Rosensweig.

1. Introduction In the magnetic hyperthermia, the high local temperatures are

Based on hyperthermia, a number of methods have been developed,
methods that are using local heat to destroy the tumour cells.
Hyperthermia can be generated in radio frequency, ultrasound and
microwave, as well as by using magnetic fluid hyperthermia. The
magnetic hyperthermia uses magnetic nanoparticles in colloidal sus-
pension subjected to the action of an alternating magnetic field to
generate local heat in the tumour tissue [1,2]. This method of cancer
therapy has certain advantages over the traditional methods: it is non-
invasive, i.e. it does not require surgery and can be applied locally, so it
does not affect the healthy cells. The conditions required to be met for
using this method, which are currently intensively investigated, are: the
magnetic nanoparticles should be biocompatible, biodegradable, with
good colloidal stability, able to be safely transportable (without clog-
ging the blood vessels) to the tumour cells, they should have high heat
generation capabilities – because they may only be used in small
quantities and limited frequency and amplitude (for patient safety), just
precise and non-invasive techniques for tracking the temperature
changes at cellular level can be used, and a deeper understanding of the
temperature effect on the biological mechanisms of the cells is also
required.
created by applying a sinusoidally varying magnetic field. When the
magnetic nanoparticles are exposed to such magnetic fields, it is gen-
erated heat to release the magnetic energy consumed for aligning the
magnetization of these nanoparticles in the direction of the applied
magnetic field. In principle, in the case of superparamagnetic particles,
two mechanisms are responsible for the dissipation of heat, i.e. the loss
of energy of the hysteresis, coming from the irreversibility of the
magnetization process – this is the case of Néel relaxation by the ro-
tation of nanoparticle magnetic moments and Brown relaxation due to
the Brownian rotation of the magnetic particles in the basic fluid. The
relaxation mechanism that dominates the magnetic behaviour of the
colloidal suspensions is determined by the nanoparticle properties.
Typically, the magnetic nanoparticles are embedded in the cellular
environment, forming agglomerations. The result is the partial blocking
of the Brownian relaxation mentioned above, as well as the decrease of
the heating efficiency [3].
The magnetic nanoparticles commonly used are those of magnetite
(Fe3O4). They are biocompatible and are eliminated from the body in a
sufficiently short time [4]. These nanoparticles can be synthesized using
various methods [1], of which the co-precipitation technique is the
most used and the most effective method of high efficiency synthesis,

⁎
Corresponding author.
E-mail address: mihaela.osaci@upt.ro (M. Osaci).

https://doi.org/10.1016/j.jmmm.2020.167451
Received 19 June 2020; Received in revised form 6 September 2020; Accepted 26 September 2020
Available online 08 October 2020
0304-8853/ © 2020 Elsevier B.V. All rights reserved.
M. Osaci and M. Cacciola
although it has a limitation related to the very wide distribution of the
nanoparticle sizes in the resulting system [1]. However, this limitation
can be avoided by current sequential centrifugation techniques [1].
The SAR value is the power dissipation per unit mass of the mag-
netic nanoparticles (or iron mass) in an applied alternating magnetic
field, being also known in the literature as specific loss power (SLP) [5].
Specific Absorption Rate (SAR) and Specific Loss Power (SLP) are used
to describe the efficiency of the method used in the treatment of cancer
by hyperthermia, when a nanofluid is involved [6]. The name of SLP is
more appropriate, because SAR is used in the context of high-frequency
radiation [7]. Low-frequency magnetic mechanisms are involved in
magnetic hyperthermia [3].
In general, the SLP values in the case of colloidal systems consisting
of commercially available nanoparticles are ranging from 4 to 100 W/g
[1]. These values strongly depend on the average size and mono-
dispersity of the nanoparticles, their structural and magnetic properties,
as well as on the frequency and amplitude of the magnetic field. [1].
When hexane was used as a dispersion medium for spherical nano-
particles with magnetic core sizes ranging from 5 to 18 nm, coated with
oleic acid for a good dispersion, the measured LSP was 230 W/g [8]. It
has been shown experimentally that the increase of the nanoparticle
monodispersivity degree by sequential centrifugation causes the in-
crease of the SLP value [1].
Recent studies show that the increase in oleic acid coating degree of
the nanoparticles leads to a decrease in their degree of agglomeration
and an increase in the local heating capacity [9].
In addition, to improve the stability of the colloidal system, for a
good circulation of the nanoparticles through the blood vessels and
avoiding the absorption of the blood proteins, and for a good adhesion
to the area containing cancer cells, we are resorting to surface func-
tionalization with organic polymer layers [10,11,14,4].
The PEG layer can limit the aggregation by minimizing the particle
interaction and avoiding the reduction of the SAR values, while the folic
acid aims to increase the adhesion of nanoparticles to the cancer cells.
The organic layer consisting of citric acid, PEG and folic acid species
behaves as an insulating shell around the nanoparticle surface
[12,13,10,11,14].
In general, a colloidal system of magnetic nanoparticles is a very
complex physical system [4]. Its behaviour is influenced by a rich set of
factors, such as: chemical composition, physical structure, nanoparticle
size distribution, nanoparticle concentration [15,16,17], nanoparticle
coating, nanoparticle magnetic anisotropy, the effect of magnetic di-
polar interaction among the nanoparticles [18], the thermal fluctua-
tions of the nanoparticle magnetic moments, the intensity of the applied
alternating magnetic field and its frequency.
The modelling and simulation play crucial roles in solving certain
problems of the colloidal system of magnetic nanoparticles used in
magnetic hyperthermia. Out of the most important heating mechanisms
used in magnetic hyperthermia, we mention: hysteresis loos (for large
sizes of nanoparticles) and magnetic relaxation loss (for super-
paramagnetic nanoparticles), [21].
In the literature, there are a lot of papers based on the simulation
models of these mechanisms. We are going to point out several models
used in the studies carried out on magnetic nanoparticle systems for
hyperthermia in the last 2 years.
The simulation of losses by magnetic hyperthermia in the magnetic
nanoparticle systems mentioned above is generally based on Monte
Carlo, Kinetic Monte Carlo and Brownian dynamics simulations. Thus,
for example, Ulrich M Engelmann predicts, by Monte Carlo simulation
of magnetic relaxation, the optimal field parameters and properties of
the magnetic nanoparticles that maximize the efficiency of the mag-
netic hyperthermia process under medical constraints [22]. Manish
Anand proposes a Monte Carlo kinetic model to study the magnetic
hysteresis by simulation in a one-dimensional chain of magnetic na-
noparticles [23]. The parameters taken into account in this model are:
the anisotropy axis orientation, dipolar interaction strength, frequency
2
Journal of Magnetism and Magnetic Materials 519 (2021) 167451
of the applied magnetic field, and temperature. Zhiyuan Zhao and
Carlos Rinaldi studied, by using Brownian dynamics simulations, the
effect of inter-particle interactions on the magnetization dynamics and
energy dissipation rates of the spherical single-domain magnetically-
blocked nanoparticles in static and alternating magnetic fields [24].
Satoshi Ota and Yasushi Takemura confirmed by simulation that the
magnetization dynamics involved in applying an alternating field are
composed of a superposition of Néel and Brownian relaxations [25].
It should be noted that in all these models the authors considered
the pre-existing static structures of the nanoparticles: linear chain of
magnetic nanoparticles or random positions of the nanoparticles in the
simulation space, without considering the self-organization of the col-
loidal magnetic nanoparticles.
In the literature, the influence of nanoparticle coating on the spe-
cific loss power is very little studied. Recently, in situ reduction method
applied for core–shell Fe3O4 with Ag and polyacrylic acid revealed that
a thin polymer coating layer had a great influence in enhancing the
hyperthermia efficiency [19]. Zavisova et al. [20] prepared and ex-
perimentally investigated Fe3O4 nanoparticles with various protein or
polymer outer-shell. They found no correlation between the layer
thickness and the magnetic hyperthermia specific adsorption rate.
In this paper, we propose a theoretical model for studying how the
nanoparticle coating affects the tendency of agglomeration of the na-
noparticles, and thus the specific loss power.
2. The correlation between the specific power loss and the coating
thickness of nanoparticles
The specific loss power (SLP) is defined as the electromagnetic
power lost per nanofluid mass unit, and it is expressed in watt per
kilogram. The SLP can be calculated in the framework of the theory of
magnetic fluid losses from Rosensweig [26], theory valid within the
range of external magnetic field amplitudes suitable for medical ap-
plications [27]. Accepting this theory, for dispersion in liquid matrix,
the volumetric power dissipation shall be expressed as follows [28]:
N i
1 2 eff 0i
p = µ 0 H0,2 ext i 2
N i=1
1+ (2 eff ) (1)
where ν is the frequency, H0, ext is the magnitude of the applied field, μ0
is the magnetic permeability of the free space, N is the number of na-
noparticles, χ0i is the equilibrium susceptibility of the i-th nanoparticle,
and eff
i
is the effective magnetic relaxation time of the i-th nanoparticle.
The effective relaxation time of the i-th nanoparticle can be described as
follows [25]:
1 1 1
i
= i
+ i
eff N B (2)
where is the Néel relaxation time, and
i
B is
the Brownian re-
i
N
laxation time.
The numerical calculation of Néel relaxation time is made taking
into account the fact that the dipolar magnetic field on the nanoparticle
and the external magnetic field are creating together a resultant mag-
netic field that does not generally act along the direction of the nano-
particle easy magnetisation axis.
This magnetic field, called local magnetic field acting on each nano-
particle, is given by the relation:
Hi = Hext + Hid (3)
In the relation (3), Hext is the external magnetic field applied, and
Hid is the internal dipolar magnetic field determined by the magnetic
dipolar interactions among the nanoparticles.
Due to the dipolar magnetic field, for the most accurate calculation
of the Néel magnetic relaxation time ( Ni ) of each nanoparticle, we can
use the Coffey method in oblique magnetic field, adapted to the local
magnetic field on a nanoparticle [29,30]. The nanoparticle Néel
M. Osaci and M. Cacciola Journal of Magnetism and Magnetic Materials 519 (2021) 167451

relaxation time in oblique magnetic fields is: 0i =3 i

i L (15)
i 1 1
4 (Si1 + Si2 )
( ) cos +
i 0N 1.47
N = i 2 1
( ci(1) (1)
1 ci2 · e
Ei12 + ci(2) (2)
1 ci2 · e
Ei21 )
(4) i =
3.4 i 3

( ) +1
1.47
i
where ΔEi12 and ΔEi21 are the normalized energy barriers for magnetic 3.4 (16)
moment re-orientations. The free diffusion time of magnetisation 0i N for
Ki vi
low damping is [29,30]: i =
kB T (17)
i vi Ms
0N =
2 kB T (5) fm Ms 1
i
L = coth( i )
th
where vi is the volume of the i nanoparticle, Ms the spontaneous H0, ext i (18)
magnetisation, kB the Boltzmann constant, T the temperature, α the
damping constant and γ the gyromagnetic ratio. µ 0 Ms vi H0, ext
=
In Eq. (4):
i
kB T (19)
ci(1p) = 2 i [cos 2 ip + hi cos( ip i )], fm is the magnetic volume fraction of the nanoparticles and H0, ext
ci(2p) = 2 i [cos2 ip + hi cos( ip i)], with p = 1, 2 (6) external amplitude of the magnetic field. fm is correlated with the vo-
Ki vi lume fraction of the nanoparticles f, according to the relation [31]:
i =
kB T (7) f
fm =
with Ki magnetic anisotropy constant of the i nanoparticle. Ψi is the
angle between Hi and the easy anisotropy axis of the ith nanoparticle. θip
th
( 1+
2
dm 2 ) (20)

is the solutions of the transcendental equation: In the relation (20), dm is the average diameter of the nanoparticles,
and δ is the thickness of the coating.
sin 2 i = 2hi sin( i i) (8)
With (1) and 15 ÷(20), for a nanofluid:
In (8) θi is the angle between magnetisation and easy anisotropy
N i
axis of the ith nanoparticle. p Ms 1 2 eff
SLP = = 3 µ0 H0, ext i coth( i) i 2
fm N i 1 + (2 eff ) (21)
µ Ms Hi i=1
hi = 0
2Ki (9) where ρ is the density of the nanoparticle material.

If hi < hic(Ψi) < 1 [29,30]: Basically, the nanoparticle coating plays an important role in the
self-organization of colloidal magnetic nanoparticles which then, by the
cos = ±1
hi2
sin2 + hi3sin2
hi4
(13 + 11 cos 2 i )sin2 nanoparticle coordinates, influences their dipolar magnetic interaction
i1,2 i i cos i i
that influences the Néel relaxation time (τiN) and the effective relaxation
2 16
hi5
+ 2
(3 + cos 2 i )sin2 i cos i time (τieff), which then goes into the SLP expression.
hi6 The nanoparticle coordinates, used to calculate the average Néel
(183 + 156 cos 2 19 cos 4 i)sin2 + ...
64 i i magnetic relaxation time (τiN) and then the effective relaxation time
(10) (τieff) for those N nanoparticles of the system, are taken after the self-
organization simulation of the colloidal magnetic nanoparticles, which
hi3
Ei12 = i [1 2hi (sin i cos i) + hi2 + 2
sin 2 i (cos i sin i) is made using the Langevin dynamics stochastic method based on an
hi4 effective Verlet-type algorithm [32]. This method starts from the nu-
+ 2
sin2 2 i+ merical resolution of the Langevin equations for the translational and
hi5 hi6 rotational motions of an i-th nanoparticle in the basic liquid [32], in
+ sin 2 i (7 cos i 3 cos 3 i 7 sin i 3 sin 3 i) + sin2 2 i+ ...]
32 2 which the random Brownian force and torque are usually modelled
(11) using the Gaussian noise [32]. The forces acting among the nano-
hi3
particles of the system are: the Van der Waals forces, the electrostatic
Ei21 = i [1 2hi (sin i + cos i) + hi2 + 2
sin 2 i (cos i + sin i) repulsive forces, the magnetic dipolar forces and the steric repulsion
hi4 forces, which have to be taken into account for the coated nano-
+ sin2 2 i+
2 particles.
hi5 hi6
+ sin 2 i (7 cos i 3 cos 3 i + 7 sin i + 3 sin 3 i) + sin2 2 i+ ...] In addition to the random Brownian torque, the conservative torque
32 2
acting on the nanoparticle is the magnetic torque. The torque acting on
(12) the i-th nanoparticle can be obtained from:
104
Si1,2 = hi sin [16 h sin + h2 (1 21 cos 2 i)
i i 3 i i
i = µ 0 [µi xHi ] (22)
hi3
+ 2
sin i (45 + 51 cos 2 i) + ...]± where μ0 is the vacuum magnetic permeability, µi is the magnetic mo-
±2 2
i h i sin 2 i (4 3hi sin i 2hi2sin2 i + ...) (13) ment of the i is the monodomain nanoparticle, usually given by [32]:

For spherical particles, analytical expression for Brownian relaxa- µi = Ms Vi µ

(23)
tion time at nonzero magnetic field is [2]: i

1+ 2 2 2 where Ms is the spontaneous magnetisation, Vi is the magnetic core

i i i i coth i
B = B0 volume, and µ is the unit vector of the magnetic moments.
i coth i 1 (14) i
Ms vi µ 0 3viH
Below is a brief presentation of these forces and moments. Next, we
In (14) i = kB T
Hi , i
B0 = kB T
, kB is the Boltzmann constant, T is briefly review the expressions of the forces and moments mentioned
the temperature, viH is the hydrodynamic volume of the i-th nano- above.
particle and η is the coefficient of dynamic viscosity. The dipolar magnetic force exerted among the magnetic moments of
For the equilibrium susceptibility χ0i, we can use the relation [28]: the nanoparticles i and j is given by [32]:

3
M. Osaci and M. Cacciola Journal of Magnetism and Magnetic Materials 519 (2021) 167451

Fmd, ij relation: [32].

3µ 0 5(µi · nij )·(mj · nij ) kB T di 2r j 1+t

= ( µi · nij )· µj + ( µj · nij )· µi + ( µi · µj )· nij nij Fsteric , ij = · ·ln · nij
4 Dij5 Dij2 t ri + r j 1 + l/2 (31)
(24) The electrostatic and steric stabilisation can be combined as elec-
For long-range magnetic dipolar interaction, we propose a direct trosteric stabilisation.
summation of the magnetic dipolar potential and forces. As can be seen in the relations (24) ÷ (31), all the types of forces
The Van der Waals' interaction force between spherical particles of listed above imply in one way or another the distance between the
radii ri and rj is [32]: centres of nanoparticles (rij), or the surface-to-surface separation be-
tween the nanoparticles, or the nanoparticle radii, or the nanoparticle
Aeff Dij (4ri rj )3 1 magnetic core radii. In expressing these dimensions, the surfactant
Fvdw = nij
6 (sij (Dij + ri + r j )) 2·(Dij2 (ri r j ) 2)2 (25) coating of the nanoparticles plays an active role.
The self-organization of colloidal nanoparticles under the action of
where nij is the versor of the direction connecting the i-th and j-th na- forces and torques (22) ÷(31) will be simulated using a Langevin dy-
noparticles, Dij is the distance between the centres of the i and j na- namics stochastic method based on an effective Verlet-type algorithm
noparticles, sij = Dij (ri + r j ) is the surface-to-surface separation be- [32]. We are going to vary the nanoparticle coating thickness to study
tween the i and j nanoparticles, and Aeff is the Hamaker effective how SLP is influenced by the nanoparticle coating thickness and
constant for iron oxide nanoparticles in water. The effective Hamaker polymer surface density, for various values of the polymer surface
constant for the iron oxide nanoparticles interacting across the water density. Then, for each thickness of the coating, the polymer surface
is Aeff = 33 − 39 10−20 J [32]. density will be varied. For each situation, the Néel magnetic relaxation
We consider that the colloidal nanoparticles possess electrical time for nanoparticles is simulated by an adapted discretized Coffey
double layers at their surfaces, and these layers cause repulsive inter- model for interacting magnetic nanoparticles, relation (4), [29,30].
actions [32]. Then, the effective magnetic relaxation time is calculated for each na-
If the normalized distancesk· sij 4 , the expression for the electro- noparticle using the relation (2), after having previously calculated the
static force is: Brown relaxation time using the relation (14). The effective magnetic
kB T 2 ri r j (1 + kDij ) relaxation time is used in the specific loss power (SLP) relation (21)
Fel, DL, ij = 4 · sij n
i· j· ·e ij obtained within the theory of magnetic fluid losses from Rosensweig
ze Dij2 (26)
[26].
If the normalized distances k· sij < 4 [32], the expression for the
electrostatic force is:
3. Results and discussions
2
ri r j e ksij
2n
Fel, DL, ij = 4 k· 2ksij
·( 01 02 ) ij For this study, we will consider the case of a colloid with elec-
ri + r j 1 e (27) trosteric stabilisation. We consider a system consisting of 50 spherical
The notations appearing in the expressions (16) and (17) are ex- magnetite nanoparticles with spontaneous magnetisation of 4.46⋅105
plained below: A/m and uniaxial magnetic anisotropy of 5⋅103 J/m3, whose sizes have
a lognormal distribution and are dispersed in water, whose dynamic
i = 4 tanh i viscosity is 8.9⋅10-4 Pa⋅s and the relative electrical permittivity is 78.5.
4 The Hamaker constant for magnetite in water is 39⋅10-20 J. The tem-
ze 0i
perature is 300 K, the coating thickness is ranging from 1 nm to 3 nm,
i = the ion concentration in solution is 1026 ions/m3, their valence is Z = 1,
kB T (28)
the surface density of the polymers ξ is ranging from 1016 m−2 to
where 0i is the surface potential of the i-th nanoparticle at infinite 4.5⋅1017 m−2, and the surface charge is 1.6⋅10-15C. The average dia-
separation, given by [32]: meter of the nanoparticles is dm = 10 nm, with a standard deviation of
q 0.1⋅dm. The chosen nanoparticle volume fraction is f = 0.05. We set the
=
0i
4 ri (1 + kri ) (29) external magnetic field intensity to 15kA/m along the Z-axis and the
frequency to 300 kHz, parameters that fall within the limits allowed for
where q is the effective charge of the particles.The thickness of the biomedical applications.
screening ionic layer κ is the inverse of the Debye constant when the Initially, we consider a random placement of the nanoparticles in a
salt concentration is 1:1. face-centred cubic grid. With the Langevin dynamics stochastic method
2e 2n 0 z 2 - Fig. 1 a)-e), we obtained an structure in the form of chains of up to 8–9
= nanoparticles (see Fig. 1d)) and aggregate of up to 26 nanoparticule
kB T (30)
(see Fig. 1d)), for the polymer surface density ξ 2.5⋅1017 m−2 and
Here, e = 1.6x10 19C (electron charge), n0 is the concentration of various values of the coating thickness.
ions in the bulk solution, z is the valence of ions in the symmetrical (z-z) In Fig. 1, we can see that the polymer concentration in the nano-
electrolyte, ε is the electrical permittivity of the solvent (for water, particle coating influences the aggregate structure of the nanoparticles.
78.5x 8.85x10 12F / m ), kB = 1.38x10 23J / K is the Boltzmann constant, and Fig. 2 shows the SLP versus the nanoparticle coating thickness, at
T is the absolute temperature. various values of the polymer surface density.
The steric interactions arise when large molecules are adsorbed on In Fig. 2, we can see that at various values of the polymer surface
the surface of the particles and prevent the direct interparticle contacts. density in the nanoparticle coating (between 1016 m−2 and 4⋅1017
Certain organic materials are usually used as steric stabilizers, espe- m−2), the SLP decreases slightly with increasing the thickness of the
cially polymers. The steric force is difficult to predict and quantify. To coating. At small thicknesses, it reaches a minimum value, after which,
define the steric force, we use the following notations: di = 2ri , at increasing values of the SLP coating thickness, it increases with in-
l = 2sij / di (sij is the separation between the surfaces), t = 2 / di (δ is the creasing coating thickness. The results can be explained by the com-
thickness of the surfactant layer), and is the surface density of the petition between the magnetostatic attraction forces (14) – directly
polymers. With these notations, for the steric force we use the following proportional to the magnetic moments of the particles and inversely

4
M. Osaci and M. Cacciola Journal of Magnetism and Magnetic Materials 519 (2021) 167451

Fig. 1. Positions of nanoparticles inside the test cube after 0.1 ms - the surface density of the polymers ξ 2.5⋅1017 m−2, a) Coating thickness = 1 nm; b) Coating
thickness = 1.5 nm; c) Coating thickness = 2 nm; d) Coating thickness = 2.5 nm; e) Coating thickness = 3 nm.

5
M. Osaci and M. Cacciola
Fig. 2. SLP versus the coating thickness of magnetic nanoparticles, at various values of the polymer surface density.
proportional to the 5th power of the interparticle distances, and the
rejection forces, mainly the steric rejection forces (21), directly pro-
portional to the thickness of the surfactant coating. For small thick-
nesses of the nanoparticle coating, the action of the steric rejection
forces is weaker and the forces of magnetostatic interaction among the
nanoparticles predominate, i.e. the tendency of agglomeration, which
means zonal volumetric concentrations of large nanoparticles. A bal-
ance is then achieved between the forces of attraction and the forces of
rejection, after which, with the increase of the nanoparticle coating
thickness, the forces of steric rejection become more pronounced. These
results confirm the experimental results published so far that are cor-
relating the coating thickness with an increase in the efficiency of the
magnetic hyperthermia process. [9,19].
Fig. 3 shows the SLP versus the surface density of the polymers at
various thicknesses of the nanoparticle coating. Regardless of the
coating thickness, SLP versus the surface density of the polymers has a
polynomial dependence of 5th order, which can be seen more clearly in
Figs. 4-8, which are also showing the data interpolation equation.
This dependence can also be explained by the competition between
the forces of rejection, especially the forces of steric rejection, and the
forces of magnetostatic attraction among the nanoparticles. As this
study reveals, the nanoparticle coating layers influence indirectly the
efficiency of the magnetic hyperthermia process by having an im-
portant role in the self-organization of the nanoparticles that influence
Fig. 3. SLP versus polymer surface density, at various values of the nanoparticle coating thickness.
6
Journal of Magnetism and Magnetic Materials 519 (2021) 167451
the intensity of the dipolar magnetic interaction, which in turn influ-
ences the value of the Néel relaxation time, as well as the SLP.
4. Conclusions
This paper provides a theoretical study on how the thickness of the
surfactant coating layer and the surface density of the polymers in the
layer are influencing the efficiency of the magnetic hyperthermia pro-
cess of a superparamagnetic system of nanoparticles in suspension in a
liquid matrix. For simulating the self-organization of colloidal nano-
particles, we use a Langevin dynamics stochastic method based on an
effective Verlet-type algorithm. The Néel relaxation time, calculated
using the Coffey model in oblique magnetic field adapted to the local
magnetic field on the nanoparticle, and the Brownian relaxation time,
calculated according to the Brown’s theory, determine an effective
magnetic relaxation time that influences the SLP, calculated according
to the linear response theory (LRT).
Following the numerical simulations, it was revealed that the SLP is
influenced either by the thickness of the nanoparticle coating layer or
by the surface density of the polymer in the layer. Thus, at a given
thickness of the coating, the SLP varies polynomially with the surface
density of the polymers in the nanoparticle coating layer. Also, it was
revealed that the SLP decreases slightly with increasing the thickness of
the coating (at small thicknesses), reaches a minimum value, after
M. Osaci and M. Cacciola Journal of Magnetism and Magnetic Materials 519 (2021) 167451

Fig. 4. SLP versus polymer surface density, at a coating thickness of 1 nm.

Fig. 5. SLP versus polymer surface density, at a coating thickness of 1.5 nm.

which, at increasing values of the coating thickness, the SLP increases cancer therapy.
with increasing coating thickness, fact confirmed by the experimental
data recently obtained in this regard.
All these behaviours of SLP caused by the thickness of the coating CRediT authorship contribution statement
layer and the polymer surface density in the layer can be explained by
the competition between the forces of rejection, mainly the steric forces Mihaela Osaci: Conceptualization, Data curation, Formal analysis,
and attraction forces, in particular the force of magnetic dipolar inter- Investigation, Methodology, Software, Writing - original draft, Writing -
action among the nanoparticles. review & editing. Matteo Cacciola: Conceptualization, Data curation,
The results described in this paper provide a control factor of the Formal analysis, Investigation, Methodology, Software, Writing - ori-
magnetic hyperthermia process by controlling the non-magnetic ginal draft, Writing - review & editing.
coating of the superparamagnetic nanoparticles, these results being
useful for optimizing the process of magnetic hyperthermia with na-
noparticles, which are of real interest as a non-invasive method in the

7
M. Osaci and M. Cacciola Journal of Magnetism and Magnetic Materials 519 (2021) 167451

Fig. 6. SLP versus polymer surface density, at a coating thickness of 2 nm.

Fig. 7. SLP versus polymer surface density, at a coating thickness of 2.5 nm.

Fig. 8. SLP versus polymer surface density, at a coating thickness of 3 nm.

8
M. Osaci and M. Cacciola
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
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