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Accepted Manuscript
Magnetic Hyperthermia Properties of Iron Oxide Nanoparticles: The Effect of Concentration Saeid Ebrahimisadr , Bagher Aslibeiki , Reza Asadi PII: DOI: Reference:
S0921-4534(17)30245-9 10.1016/j.physc.2018.02.014 PHYSC 1253271
To appear in:
Physica C: Superconductivity and its applications
Received date: Accepted date:
10 July 2017 28 February 2018
Please cite this article as: Saeid Ebrahimisadr , Bagher Aslibeiki , Reza Asadi , Magnetic Hyperthermia Properties of Iron Oxide Nanoparticles: The Effect of Concentration, Physica C: Superconductivity and its applications (2018), doi: 10.1016/j.physc.2018.02.014
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
Highlights Fe3O4 nanoparticles were prepared by co-precipitation method. Effect of concentration on hyperthermia properties was investigated. Specific absorption rate remain almost constant with variation of concentration. Heat generation in AC magnetic field is strongly depends on concentration.
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Magnetic Hyperthermia Properties of Iron Oxide Nanoparticles: The Effect of Concentration Saeid Ebrahimisadr, Bagher Aslibeiki, Reza Asadi Department of Physics, University of Tabriz, Tabriz, Iran [email protected], [email protected], [email protected]
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Abstract We investigated the effect of concentration on magnetic hyperthermia properties of Fe3O4 nanoparticles (NPs). The NPs were synthesized by co-precipitation method at 80 °C. Scanning electron microscope image showed that the mean diameter of NPs is about 18 nm. The XRD pattern indicated that the sample is pure Fe3O4 with spinel structure and the FT-IR spectroscopy confirmed formation of metal-oxygen bonds in the octahedral and tetrahedral spinel sub-lattice which further confirmed crystalline structure of the sample. The hyperthermia property of Fe3O4 NPs was investigated via an induction heater generating alternating magnetic field with frequency of 92 kHz. The temperature rise (T) of suspension in the AC magnetic field was studied on different concentrations of NPs and the specific absorption rate (SAR) was obtained from Box-Lucas equation and linear fitting of T‒time curve. The results showed that the T sharply increases with increasing the NPs concentration while the SAR remains almost constant. Keywords: Fe3O4 nanoparticle; Magnetic hyperthermia; Concentration; Co-precipitation.
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1. Introduction In recent years, magnetic iron oxide NPs have been attracting great interest due to their remarkable possibilities and potential applications such as high density magnetic recording media, colored pigments [1] and as a ferrofluid they have abundant in-vivo applications like magnetic resonance imaging (MRI) as contrast agents, separation cells, magnetic drug targeting and delivery, and especially they can generate heat in an alternating magnetic field and become promising material for tumor hyperthermia [2, 3]. In magnetic hyperthermia, Fe3O4 NPs are exposed to an alternating (AC) magnetic field in which the NPs oscillate with the applied AC field. For Hyperthermia to occur there must be energy dissipation to convert the magnetic field energy into heat. Two distinct types of dissipation in magnetic NPs can contribute to hyperthermia are: (a) Néel relaxation, that is, the fluctuation of a magnetic moment of NPs over an anisotropic energy barrier and (b) Brown relaxation to viscous losses due to particle reorientation in solution [4]. The heating capacity of magnetic NPs is quantified by the specific absorption rate (SAR), which accounts for the heating power per mass unit of dissipating material [5]. The factors which determine and influence the SAR value are magnetic NPs anisotropy constant, saturation magnetization, particle size, phase composition, shape and AC magnetic field parameters like frequency and amplitude [6]. The concentration of NPs can strongly affect the heat generation of magnetic nanoparticles and SAR value. Therefore, in this study we investigated the effect of NPs concentration on magnetic hyperthermia properties of Fe3O4 NPs. 2. Experimental Details 2.1. Synthesis Fe3O4 NPs were synthesized by co-precipitation method. For fabrication of Fe3O4 NPs we used 2.703 g of FeCl3.6H2O and 0.994 g of FeCl2.4H2O. The salts were dissolved in 50 ml distilled water at 80 ﹾC under air atmosphere. After 15 minutes stirring the solution, aqueous sodium hydroxide
ACCEPTED MANUSCRIPT (NaOH) was added to the solution to precipitate the Fe3O4 NPs. After 30 minutes of stirring, the prepared Iron Oxide NPs were magnetically separated from the solution and then washed for three times with distilled water to remove impurities from the solution [3]. The chemical reaction of Fe3O4 formation is written as following equation: FeCl2.4H2O + 2(FeCl3.6H2O) + 8NaOH → Fe3O4 + 8NaCl +20H2O
(1)
2.2. Measurements
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Fe3O4 NPs were characterized by X-ray diffraction (XRD) with Cu-Kα radiation using Philips X’PERT MPD. In order to study the morphology of NPs the FESEM image was taken by using MIRA3 TESCAN microscope. FT-IR analysis was performed using Bruker EQ55/5spectrometer to characterize the surface nature of Fe3O4 NPs with KBr discs in the range of 4000-400 cm-1 on Fourier transfer infrared. Magnetic hyperthermia and heat generation of Fe3O4 NPs were studied using a homemade induction heater with the frequency of 92 kHz. 3. Results and discussions All the observed peaks in XRD pattern (Figure 1) are proof of spinel structure of Fe3O4 NPs. The crystallite size was determined by Debye-Scherer equation to be around 10.4±1.8 nm.
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(2)
is full-width at half-
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Where k (≈ 0.9) is the Schererˈs constant, is the wavelength of the x-ray, maximum of the diffraction peaks and is Braggˈs angle.
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Fig 1. XRD Pattern of Fe3O4 NPs.
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Figure 2 shows the FESEM image of the Fe3O4 NPs. The image indicates formation of uniform size distribution of NPs. A log-normal function was used to determine the mean particles size as below
√
{
[
⁄
]
}
(3)
where is the most probable particle diameter and is the width of the distribution. The value of average particle diameter, , is 18.09 nm which is larger than the crystallite size determined by XRD. The difference between < D XRD > and < D SEM > could be attributed to aggregation of particles and surface spin disorder [7]. The EDX spectra image (figure 2.b) confirms the presence of Fe and O elements in Fe3O4 NPs sample.
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Fig 2. (a) FESEM image and (b) EDX spectra of Fe3O4 NPs.
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According to figure 3, the FT-IR spectra indicates huge absorption around the peak 3435 cm-1 which is related to the –OH Stretching. At 1635 cm-1, H-O-H bonding is seen as a peak and the main peaks at 575 cm-1 and 664 cm-1 is related to Fe-O stretching at octahedral and tetrahedral sub lattice [8].
Fig 4. The experimental set-up for hyperthermia
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Fig 3. FT-IR spectra of Fe3O4 NPs. measurements.
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To study the heat generation of samples, we put the suspensions of NPs inside a cupper coil which applies AC magnetic field to the samples (figure 4) for approximately 15 minutes.
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Figure 5 shows the ∆T vs. time curves of the samples with different concentrations of Fe3O4 NPs. It is observed that with the increase of concentration the heat generation increases, respectively. Magnetic energy dissipation in a ferrofluid sample is measured in terms of specific absorption rate (SAR) as below (4)
Where Ms is mass of suspension including distilled water and NPs, Mn is mass of Fe3O4 NPs, C is the specific heat capacity of distilled water and
is the initial linear slope of the ∆T-time curves.
The SAR value were obtained using two fitting methods first using linear fitting (Eq.4) and second, using Box Lucas fitting { } as the following equation: (5)
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Fig 5. Temperature rise of Fe3O4 suspension Fig 6. SAR as a function of concentration. with different concentrations in an AC magnetic field. Figure 5 shows that the temperature increases up to 58 in a sample with concentration of 12.5% and 9 with concentration of 1% which means temperature rise of Fe3O4 NPs strongly depends on concentration. On the other hand, figure 6 shows that the obtained SAR values of samples with linear fitting and Box Lucas fitting are approximately in same range and the SAR values is almost independent form concentration of NPs.
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3. Conclusions In this study we investigated the effect of concentration on magnetic hyperthermia properties of iron oxide NPs. Results showed that the maximum temperature rise is 58 for sample with concentration of 12.5% and the minimum value is 9 in concentration of 1%. The obtained results for SAR values using two different method, Box-Lucas and linear fitting of ∆T vs. time curves, confirm negligible effect of concentration on SAR value. References
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[1] Y. Huang, L. Zhang, W. Huan, X. Liang, X. Liu, Y. Yang, Glass Physics and Chemistry, 36 (2010) 325-331. [2] C. Alves, R. Aquino, J. Depeyrot, F.A. Tourinho, E. Dubois, R. Perzynski, J. Mater. Sci., 42 (2007) 22972303. [3] P.H. Linh, P. Van Thach, N.A. Tuan, N.C. Thuan, N.X. Phuc, in: Journal of Physics: Conference Series, IOP Publishing, 2009, pp. 012069. [4] D. Serantes, D. Baldomir, C. Martinez-Boubeta, K. Simeonidis, M. Angelakeris, E. Natividad, M. Castro, A. Mediano, D.X. Chen, A. Sanchez, L.I. Balcells, B. Martinez, J. Appl. Phys., 108 (2010) 073918-073915. [5] A. Urtizberea, E. Natividad, A. Arizaga, M. Castro, A. Mediano, J. Phys. Chem.: C, 114 (2010) 4916-4922. [6] B. Mehdaoui, A. Meffre, J. Carrey, S. Lachaize, L.-M. Lacroix, M. Gougeon, B. Chaudret, M. Respaud, Adv. Funct. Mater., 21 (2011) 4573-4581. [7] B. Aslibeiki, Curr. Appl. Phys., 14 (2014) 1659-1664. [8] J. Sun, S. Zhou, P. Hou, Y. Yang, J. Weng, X. Li, M. Li, Journal of biomedical materials research Part A, 80 (2007) 333-341.
Magnetic Hyperthermia Properties of Iron Oxide Nanoparticles: The Effect of Concentration Saeid Ebrahimisadr , Bagher Aslibeiki , Reza Asadi PII: DOI: Reference:
S0921-4534(17)30245-9 10.1016/j.physc.2018.02.014 PHYSC 1253271
To appear in:
Physica C: Superconductivity and its applications
Received date: Accepted date:
10 July 2017 28 February 2018
Please cite this article as: Saeid Ebrahimisadr , Bagher Aslibeiki , Reza Asadi , Magnetic Hyperthermia Properties of Iron Oxide Nanoparticles: The Effect of Concentration, Physica C: Superconductivity and its applications (2018), doi: 10.1016/j.physc.2018.02.014
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
Highlights Fe3O4 nanoparticles were prepared by co-precipitation method. Effect of concentration on hyperthermia properties was investigated. Specific absorption rate remain almost constant with variation of concentration. Heat generation in AC magnetic field is strongly depends on concentration.
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ACCEPTED MANUSCRIPT
Magnetic Hyperthermia Properties of Iron Oxide Nanoparticles: The Effect of Concentration Saeid Ebrahimisadr, Bagher Aslibeiki, Reza Asadi Department of Physics, University of Tabriz, Tabriz, Iran [email protected], [email protected], [email protected]
AN US
CR IP T
Abstract We investigated the effect of concentration on magnetic hyperthermia properties of Fe3O4 nanoparticles (NPs). The NPs were synthesized by co-precipitation method at 80 °C. Scanning electron microscope image showed that the mean diameter of NPs is about 18 nm. The XRD pattern indicated that the sample is pure Fe3O4 with spinel structure and the FT-IR spectroscopy confirmed formation of metal-oxygen bonds in the octahedral and tetrahedral spinel sub-lattice which further confirmed crystalline structure of the sample. The hyperthermia property of Fe3O4 NPs was investigated via an induction heater generating alternating magnetic field with frequency of 92 kHz. The temperature rise (T) of suspension in the AC magnetic field was studied on different concentrations of NPs and the specific absorption rate (SAR) was obtained from Box-Lucas equation and linear fitting of T‒time curve. The results showed that the T sharply increases with increasing the NPs concentration while the SAR remains almost constant. Keywords: Fe3O4 nanoparticle; Magnetic hyperthermia; Concentration; Co-precipitation.
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1. Introduction In recent years, magnetic iron oxide NPs have been attracting great interest due to their remarkable possibilities and potential applications such as high density magnetic recording media, colored pigments [1] and as a ferrofluid they have abundant in-vivo applications like magnetic resonance imaging (MRI) as contrast agents, separation cells, magnetic drug targeting and delivery, and especially they can generate heat in an alternating magnetic field and become promising material for tumor hyperthermia [2, 3]. In magnetic hyperthermia, Fe3O4 NPs are exposed to an alternating (AC) magnetic field in which the NPs oscillate with the applied AC field. For Hyperthermia to occur there must be energy dissipation to convert the magnetic field energy into heat. Two distinct types of dissipation in magnetic NPs can contribute to hyperthermia are: (a) Néel relaxation, that is, the fluctuation of a magnetic moment of NPs over an anisotropic energy barrier and (b) Brown relaxation to viscous losses due to particle reorientation in solution [4]. The heating capacity of magnetic NPs is quantified by the specific absorption rate (SAR), which accounts for the heating power per mass unit of dissipating material [5]. The factors which determine and influence the SAR value are magnetic NPs anisotropy constant, saturation magnetization, particle size, phase composition, shape and AC magnetic field parameters like frequency and amplitude [6]. The concentration of NPs can strongly affect the heat generation of magnetic nanoparticles and SAR value. Therefore, in this study we investigated the effect of NPs concentration on magnetic hyperthermia properties of Fe3O4 NPs. 2. Experimental Details 2.1. Synthesis Fe3O4 NPs were synthesized by co-precipitation method. For fabrication of Fe3O4 NPs we used 2.703 g of FeCl3.6H2O and 0.994 g of FeCl2.4H2O. The salts were dissolved in 50 ml distilled water at 80 ﹾC under air atmosphere. After 15 minutes stirring the solution, aqueous sodium hydroxide
ACCEPTED MANUSCRIPT (NaOH) was added to the solution to precipitate the Fe3O4 NPs. After 30 minutes of stirring, the prepared Iron Oxide NPs were magnetically separated from the solution and then washed for three times with distilled water to remove impurities from the solution [3]. The chemical reaction of Fe3O4 formation is written as following equation: FeCl2.4H2O + 2(FeCl3.6H2O) + 8NaOH → Fe3O4 + 8NaCl +20H2O
(1)
2.2. Measurements
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Fe3O4 NPs were characterized by X-ray diffraction (XRD) with Cu-Kα radiation using Philips X’PERT MPD. In order to study the morphology of NPs the FESEM image was taken by using MIRA3 TESCAN microscope. FT-IR analysis was performed using Bruker EQ55/5spectrometer to characterize the surface nature of Fe3O4 NPs with KBr discs in the range of 4000-400 cm-1 on Fourier transfer infrared. Magnetic hyperthermia and heat generation of Fe3O4 NPs were studied using a homemade induction heater with the frequency of 92 kHz. 3. Results and discussions All the observed peaks in XRD pattern (Figure 1) are proof of spinel structure of Fe3O4 NPs. The crystallite size was determined by Debye-Scherer equation to be around 10.4±1.8 nm.
AN US
(2)
is full-width at half-
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ED
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Where k (≈ 0.9) is the Schererˈs constant, is the wavelength of the x-ray, maximum of the diffraction peaks and is Braggˈs angle.
CE
Fig 1. XRD Pattern of Fe3O4 NPs.
AC
Figure 2 shows the FESEM image of the Fe3O4 NPs. The image indicates formation of uniform size distribution of NPs. A log-normal function was used to determine the mean particles size as below
√
{
[
⁄
]
}
(3)
where is the most probable particle diameter and is the width of the distribution. The value of average particle diameter, , is 18.09 nm which is larger than the crystallite size determined by XRD. The difference between < D XRD > and < D SEM > could be attributed to aggregation of particles and surface spin disorder [7]. The EDX spectra image (figure 2.b) confirms the presence of Fe and O elements in Fe3O4 NPs sample.
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Fig 2. (a) FESEM image and (b) EDX spectra of Fe3O4 NPs.
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According to figure 3, the FT-IR spectra indicates huge absorption around the peak 3435 cm-1 which is related to the –OH Stretching. At 1635 cm-1, H-O-H bonding is seen as a peak and the main peaks at 575 cm-1 and 664 cm-1 is related to Fe-O stretching at octahedral and tetrahedral sub lattice [8].
Fig 4. The experimental set-up for hyperthermia
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Fig 3. FT-IR spectra of Fe3O4 NPs. measurements.
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To study the heat generation of samples, we put the suspensions of NPs inside a cupper coil which applies AC magnetic field to the samples (figure 4) for approximately 15 minutes.
AC
Figure 5 shows the ∆T vs. time curves of the samples with different concentrations of Fe3O4 NPs. It is observed that with the increase of concentration the heat generation increases, respectively. Magnetic energy dissipation in a ferrofluid sample is measured in terms of specific absorption rate (SAR) as below (4)
Where Ms is mass of suspension including distilled water and NPs, Mn is mass of Fe3O4 NPs, C is the specific heat capacity of distilled water and
is the initial linear slope of the ∆T-time curves.
The SAR value were obtained using two fitting methods first using linear fitting (Eq.4) and second, using Box Lucas fitting { } as the following equation: (5)
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Fig 5. Temperature rise of Fe3O4 suspension Fig 6. SAR as a function of concentration. with different concentrations in an AC magnetic field. Figure 5 shows that the temperature increases up to 58 in a sample with concentration of 12.5% and 9 with concentration of 1% which means temperature rise of Fe3O4 NPs strongly depends on concentration. On the other hand, figure 6 shows that the obtained SAR values of samples with linear fitting and Box Lucas fitting are approximately in same range and the SAR values is almost independent form concentration of NPs.
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3. Conclusions In this study we investigated the effect of concentration on magnetic hyperthermia properties of iron oxide NPs. Results showed that the maximum temperature rise is 58 for sample with concentration of 12.5% and the minimum value is 9 in concentration of 1%. The obtained results for SAR values using two different method, Box-Lucas and linear fitting of ∆T vs. time curves, confirm negligible effect of concentration on SAR value. References
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[1] Y. Huang, L. Zhang, W. Huan, X. Liang, X. Liu, Y. Yang, Glass Physics and Chemistry, 36 (2010) 325-331. [2] C. Alves, R. Aquino, J. Depeyrot, F.A. Tourinho, E. Dubois, R. Perzynski, J. Mater. Sci., 42 (2007) 22972303. [3] P.H. Linh, P. Van Thach, N.A. Tuan, N.C. Thuan, N.X. Phuc, in: Journal of Physics: Conference Series, IOP Publishing, 2009, pp. 012069. [4] D. Serantes, D. Baldomir, C. Martinez-Boubeta, K. Simeonidis, M. Angelakeris, E. Natividad, M. Castro, A. Mediano, D.X. Chen, A. Sanchez, L.I. Balcells, B. Martinez, J. Appl. Phys., 108 (2010) 073918-073915. [5] A. Urtizberea, E. Natividad, A. Arizaga, M. Castro, A. Mediano, J. Phys. Chem.: C, 114 (2010) 4916-4922. [6] B. Mehdaoui, A. Meffre, J. Carrey, S. Lachaize, L.-M. Lacroix, M. Gougeon, B. Chaudret, M. Respaud, Adv. Funct. Mater., 21 (2011) 4573-4581. [7] B. Aslibeiki, Curr. Appl. Phys., 14 (2014) 1659-1664. [8] J. Sun, S. Zhou, P. Hou, Y. Yang, J. Weng, X. Li, M. Li, Journal of biomedical materials research Part A, 80 (2007) 333-341.