PVA and EDTA grafted superparamagnetic Ni doped iron oxide nanoparticles prepared by constant current electrodeposition for biomedical applications

Journal of Nanoanalysis

مقاله 8، دوره 6، شماره 2، شهریور 2019، صفحه 138-144   

نوع مقاله: Original Research Paper

شناسه دیجیتال (DOI): 10.22034/jna.2019.667137

نویسندگان

Mustafa Aghazadeh^{* 1}؛ Isa Karimzadeh^{* 2}؛ Mohammad Reza Ganjali³

¹Materials and Nuclear Research School, Nuclear Science and Technology Research Institute (NSTRI), Tehran, Iran

²Department of Physics, Faculty of Science, Central Tehran Branch, Islamic Azad University, Tehran, Iran

³Center of Excellence in Electrochemistry, University of Tehran, Tehran, Iran

چکیده

In this paper, a rapid and room temperature electrochemical method is introduced in preparation of Ni doped iron oxide nanoparticles (Ni-IONs) grafted with ethylenediaminetetraacetic acid (EDTA) and polyvinyl alcohol (PVA). EDTA/Ni-IONs and PVA/Ni-IONs samples were prepared through base electro-generation on the cathode surface from aqueous solution of iron(II) chloride, iron(III) nitrate and nickel chloride salts with EDTA/PVA additive. Uniform and narrow particle size Ni-IONs with an average diameter of 15 nm was achieved. Ni doping into the crystal structure of synthesized IONs and also surface grafting with EDTA/or PVA were established through FT-IR and EDAX analyses. The saturation magnetization values for the resulting EDTA/Ni-IONs and PVA/Ni-IONs were found to be 38.03 emu/g and 33.45 emu/g, respectively, which proved their superparamagnetic nature in the presence of applied magnetic field. The FE-SEM observations, XRD and VSM data confirmed the suitable size, crystal structure and magnetic properties of the prepared samples for uses in biomedical aims.
 

کلیدواژه‌ها

Electrochemical Synthesis؛ Iron Oxide؛ Nanoparticles, Ni Doping؛ Surface Grafting

سایر فایل های مرتبط با مقاله

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اصل مقاله

INTRODUCTION

Iron oxide nanoparticles (IONs) have tremendous attention for their excellent physicochemical characteristics and engaged biomedical uses. Recently, IONs have been investigated as the diagnostic and therapeutic agents in magnetic hyperthermia, bio-sensing, cancer therapy, etc. [1-3]. IONs are a proper medical nano-material type due to their high surface area, superparamagnetic nature, and high magnetization values [4]. Among IONs, magnetite (Fe₃O₄) is promising case for in vivo and in vitro therapies [5]. In this regard, development of new synthesis routes for fabrication of the naked and coated IONs are very interesting [6]. The most common methods applied to produce high-quality IONs are hydrothermal, thermal decomposition and co-precipitation protocols [7,8], which need to special pressure and temperature synthesis conditions. Recently, electrochemical synthesis has been also mentioned as a simple and non-expensive method for fabrication of pure and metal-ion doped IONs [9-16]. Electrochemical synthesis provides a low cost and simple route to prepare nano-materials [17-20].

It was reported that surface modification plays critical role in the development of any magnetic NPs platform for biomedical uses. In this regard, coating with polymers (like PEG, PVA, PEI and chitosan [21-26]) are preferred due to the (1) balance the magnetic interaction and (2) improve the biocompatibility [23,24]. Up now, metal ion doping has been also used to improve the superparamagnetic behavior of IONs [27,28]. Here, PVA- and EDTA- grafted Ni doped IONs (i.e. PVA/Ni-IONs and EDTA/Ni-IONs) were prepared using a novel one-pot electrochemical strategy. The galvanostatic Cathodic was chosen for the preparation of samples. In this method, the morphology and crystal structure of the products could be easily changed through altering the applied current, potential and electrolyte composition [29-31]. The prepared samples were analyzed using FT-IR, FE-SEM, XRD and VSM techniques.

EXPERIMENTAL PROCEDURE

Materials

Iron (III) nitrate nonahydrate (Fe(NO₃)₃ .6H₂O), Iron (II) chloride tetrachloride (FeCl₂ .4H₂O), nickel chloride hexahydrate (NiCl₂ .4H₂O), polyvinyl alcohol (PVA) and (ethylenediaminetetraacetic acid disodium salt dehydrate (EDTA-Na₂, 99.9%) were purchased from Sigma-Aldrich. The graphite plates and stainless steel sheets (316L) were provided from local companies.

Preparation of PVA/Ni-IONs and EDTA/Ni-IONs

The cathodic electro-deposition was applied as a preparation route for the fabrication of PVA/Ni-IONs and EDTA/Ni-IONs samples. The deposition bath solution was the iron(II) chloride/iron(III) nitrate/nickel chloride salts (0.2g:0.5g:0.05g, respectively) dissolved in 200 cc deionized H₂O. In the deposition of PVA/Ni-IONs, polyvinyl alcohol (0.1g) was added into the above mentioned deposition bath and stirred for 10min, and the electro-synthesis run was then performed. For preparation of EDTA/Ni-IONs sample, ethylenediaminetetraacetic acid disodium salt (0.1g) was added into the electrolyte and stirred for 10min. The electrochemical set up was composed of two-electrode system containing a 4cm*2cm stainless steel cathode centered between two graphite plates (4cm*2cm). In the deposition of both samples, constant current deposition mode (i= 5 mA cm^-2), deposition time of 30 min and T=25^oC were the electro-synthesis conditions. After 30min deposition in the above mentioned electrochemical set-up, a black film was deposited on the steel cathode in both deposition syntheses. At the end of deposition time, the cathode sheet was removed from the deposition bath and washed with ethanol several times. Then, the black film was scraped from the cathode and dispersed in the 50 cc ethanol (96%), and centrifuged at 3000rpm for 5min (to remove the free- and unattached PVA/or EDTA onto the IONs). In final, the black powder was collected from the ethanol solution by magnet and dried at 70 ^oC (in vacuum oven) for 20min. The obtained products were labeled EDTA/-Ni-IONs and PVA/Ni-IONs samples and analyzed through various techniques.

Characterization techniques

The XRD patterns of the fabricated samples were collected at room temperature using a Phillips PW-1800 X-ray diffractometer equipped with a Cu Kα radiation source (λ = 0.154056 nm). The IR spectra were provided using Bruker Vector 22 IR spectrometer in the frequency range 4,000–400 cm⁻¹. Field-emission Scanning Electron Microscope (FE-SEM, model Mira 3-XMU with accelerating voltage of 100 kV), attached with Energy Dispersive X-ray Spectroscopy (EDAX, for measuring elemental composition) were used for observing the surface morphology and collecting elemental data. Magnetization measurements were performed at room temperature with vibrating sample magnetometer (VSM, Lakeshore 4710).

RESULTS AND DISCUSSION

Crystal structure

Fig. 1 shows the resulted patterns for the prepared EDTA/-Ni-IONs and PVA/Ni-IONs samples from XRD analysis. In both XRD patterns, the diffraction peaks of (111), (220), (311), (400), (422), (511), (440) and (533) are observed at 2theta of 18.35º, 31.06º, 36.24º, 43.18º, 53.81º, 57.02º and 74.24º, respectively. These peaks in the diffraction patterns correspond to the inverse cubic spinel structure of the magnetite phase with a lattice parameter a₀ = 8.394 Å. The identification of the crystalline phase was performed by comparing our results with the PDF card (85-1436). As the chemical nature of both samples are the same, i.e. Ni cations doped iron oxide. Hence, it is expected that the XRD patterns of both samples are identical with some differences in the peak intensities. Our XRD data proved this fact, where the magnetite crystal structure is observed for both samples. Notably, the surface coat on the surface of Ni-IONs has no essential change on the XRD patterns of Ni-IONs. The Debye–Scherrer formula was used to obtain the average diameter from the most intense peak in Figs. 1a-b (i.e. (311) diffraction peaks), and yielded the D_(hkl) values of 9.4nm and 10.1nm for the fabricated EDTA/-Ni-IONs and PVA/Ni-IONs samples, respectively.

FT-IR

The surface chemical structures of the EDTA/Ni-IONs and PVA/Ni-IONs samples were characterized by Fourier transform infrared (FTIR) spectroscopy (Fig. 2). This was used to prove the EDTA and PVA is grafted onto the Ni-IONs. In both spectra, the IR absorption bands at about 592 cm^-1 and 554 cm^-1 are attributed to Fe–O stretching vibration for the IONs [32,33]. Also, the broad bands at about 3400-3450 cm^-1 are ascribed to the –OH groups of water, PVA and EDTA, and those originally on the surface of the IONs [34]. These data verified the magnetite structure for both EDTA/Ni-IONs and PVA/Ni-IONs samples.

For the EDTA grafted Ni-IONs sample, the following IR bands are also observed in Fig. 2a; (1) C–N and C–C stretching vibrations at 1097 cm⁻¹ and 916 cm^–1, respectively [34], (2) C-O scissoring vibration at 1661 cm⁻¹ [35], (3) -CH₂ and C-H stretching and waging vibration modes at 1393 cm⁻¹, 1311 cm⁻¹ and 1168 cm⁻¹ [36], (4) N–C-H asymmetric stretching at 2862 cm^-1 [37,38], (5) C=O and C-OH stretching vibrations at 1585 cm⁻¹ and 1481 cm⁻¹, respectively [36,38] and (6) the C-H stretching of CH₂ groups at 2978 cm⁻¹ and 2926 cm⁻¹ [36-38]. These IR results clearly indicated the EDTA is grafted onto Ni-IONs surfaces.

For the prepared PVA/Ni-IONs sample (Fig. 2b), the following vibrations related to PVA are observed; (i) two vibrations at 2954 cm⁻¹ and 2909 cm⁻¹ due to C-H in CH₂ groups [39], (ii) the twisting and wagging vibrations of the CH₃ group at 1168 and 1377 cm^–1 [40,41], (iii) the adsorbed water,vibration band at 1624 cm⁻¹ and C-C vibration at 1095 cm⁻¹ [42], (iv) the stretching and waging vibration modes of CH₂ and C-H bonds at 1465 cm⁻¹, 1262 cm⁻¹ and 1119 cm⁻¹ [43], and (v) CH₂ rocking at 916 cm⁻¹ [43,44]. These data revealed the presence of PVA onto Ni-IONs.

Morphological characterization

Morphology of the prepared samples was examined through FESEM technique and their chemical composition was detected by EDAX analysis. FESEM observations of the surface morphology of both samples showed particle texture with spherical shape (Figs. 3a and b). It was also observed the fabricated EDTA/Ni-IONs and PVA/Ni-IONs samples have a particle size range of 10-15nm (Figs. 3a-b). The EDAX plots and the extracted data are further showed in Figs. 3c and d. For the EDTA/Ni-IONs sample, the presence of oxygen, carbon, nitrogen, iron and nickel elements with weight percentage of 39.02%, 13%, 2.3%, 35.28% and 10.4% are respectively observed. From these data, the doping of iron oxide by Ni cations and their surface coating with EDTA were clearly proved. About PVA/Ni-IONs sample, the oxygen (48.79 wt%), carbon (11.84 wt%), iron (32.19 wt%) and nickel (7.18 wt%) were detected. These data revealed the PVA grafting onto iron oxide and its doping with Ni cations during electrodeposition.

Magnetic evaluation

Magnetic properties of the electrosynthesized iron oxides were studied using their M–H curves. M–H curves of EDTA and PVA grafted Ni-IONs samples are shown in Fig. 4. The saturation magnetization (Ms), coercivity (Hci) and remenance magnetization (Mr) values calculated from the M–H curves for both Ni-IONs samples are also listed in Table 1. The M–H curves clearly showed superparamagnetic nature of both samples at 300K since Hci and Mr values are very negligible (as seen in Fig. 4b). Superparamagnetic behavior of IONs at room temperature is very useful in in vivo uses as they do not retain magnetization before and after exposure to an external magnetic field [45]. The superparamagnetic nature is mainly results from the small size of IONs, where their sizes (as observed in FE-SEM observations in Figs. 3a,b) are smaller than the superparamagnetic critical size (i.e. 20nm) [46]. From M-H profiles, the Ms values of EDTA/Ni-IONs and PVA/Ni-IONs were observed to be 38.03 emu/g and 33.45 emu/g, respectively, which are smaller than those reported to electrosynthesized bare IONs (Ms=82.3 emu/g [47], and bare Ni-IONs (Ms=47.25 emu/g [33]), which reflect the reduction of magnetite portion in the coated samples due to non-magnetic EDTA/or PVA layer. However, the observed Ms values showed the proper magnetic response of our samples in the presence of an applied field. Furthermore, the prepared samples exhibited negligible Mr values (Mr=0.36 emu/g for EDTA/Ni-IONs and Mr=0.21 for PVA/Ni-IONs), which verified their initial suitability for biomedical uses like as hyperthermia.

CONCLUSION

In summary, Ni²⁺ doped iron oxide nanoparticles were successfully synthesized using the cathodic deposition and their surface was in situ grafted with EDTA and PVA agents, leading to formation of EDTA/Ni-IONs and PVA/Ni-IONs. The XRD data proved phase purity of the electrosynthesized IONs. FTIR results confirmed the chemical composition of the samples, and VSM evaluation exhibited the superparamagnetic nature for the prepared Ni-IONs.

CONFLICT OF INTEREST

The authors declare that there is no conflict of interests regarding the publication of this manuscript.

 

مراجع

 

1. Chen J, Ning C, Zhou Z, Yu P, Zhu Y, Tan G, et al. Nanomaterials as photothermal therapeutic agents. Progress in Materials Science. 2019;99:1-26.

2. Zhu L, Zhou Z, Mao H, Yang L. Magnetic nanoparticles for precision oncology: theranostic magnetic iron oxide nanoparticles for image-guided and targeted cancer therapy. Nanomedicine. 2017;12(1):73-87.

[3] S. V. Spirou, M. Basini, A. Lascialfari, C. Sangregorio and C. Innocenti, Biodistribution and Toxicity of Micellar Platinum Nanoparticles in Mice via Intravenous Administration, Nanomater. 8(6), 401-422 (2018). doi: 10.3390/nano8060410

4. Ha Y, Ko S, Kim I, Huang Y, Mohanty K, Huh C, et al. Recent Advances Incorporating Superparamagnetic Nanoparticles into Immunoassays. ACS Applied Nano Materials. 2018;1(2):512-21.

5. Xie W, Guo Z, Gao F, Gao Q, Wang D, Liaw B-s, et al. Shape-, size- and structure-controlled synthesis and biocompatibility of iron oxide nanoparticles for magnetic theranostics. Theranostics. 2018;8(12):3284-307.

6. Karimzadeh I, Dizaji HR, Aghazadeh M. Development of a facile and effective electrochemical strategy for preparation of iron oxides (Fe3O4 and γ-Fe2O3) nanoparticles from aqueous and ethanol mediums and in situ PVC coating of Fe3O4 superparamagnetic nanoparticles for biomedical applications. Journal of Magnetism and Magnetic Materials. 2016;416:81-8.

7. Aghazadeh M, Ganjali MR. Starch-assisted electrochemical fabrication of high surface area cobalt hydroxide nanosheets for high performance supercapacitors. Journal of Materials Science: Materials in Electronics. 2017;28(15):11406-14.

8. Wu W, Wu Z, Yu T, Jiang C, Kim W-S. Recent progress on magnetic iron oxide nanoparticles: synthesis, surface functional strategies and biomedical applications. Science and Technology of Advanced Materials. 2015;16(2):023501.

9. Aghazadeh M, Karimzadeh I, Ganjali MR, Mohebi Morad M. A novel preparation method for surface coated superparamagnetic Fe3O4 nanoparticles with vitamin C and sucrose. Materials Letters. 2017;196:392-5.

10. Aghazadeh M, Ganjali MR. Samarium-doped Fe3O4 nanoparticles with improved magnetic and supercapacitive performance: a novel preparation strategy and characterization. Journal of Materials Science. 2017;53(1):295-308.

11. Aghazadeh M, Karimzadeh I, Ganjali MR. Electrochemical evaluation of the performance of cathodically grown ultra-fine magnetite nanoparticles as electrode material for supercapacitor applications. Journal of Materials Science: Materials in Electronics. 2017;28(18):13532-9.

12. Aghazadeh M, Karimzadeh I, Ganjali MR, Behzad A. Mn2+-doped Fe3O4 nanoparticles: a novel preparation method, structural, magnetic and electrochemical characterizations. Journal of Materials Science: Materials in Electronics. 2017;28(23):18121-9.

13. Aghazadeh M, Ganjali MR. Evaluation of supercapacitive and magnetic properties of Fe3O4 nano-particles electrochemically doped with dysprosium cations: Development of a novel iron-based electrode. Ceramics International. 2018;44(1):520-9.

14. Aghazadeh M, Ganjali MR. One-pot electrochemical synthesis and assessment of super-capacitive and super-paramagnetic performances of Co2+ doped Fe3O4 ultra-fine particles. Journal of Materials Science: Materials in Electronics. 2017;29(3):2291-300.

15. Aghazadeh M, Karimzadeh I, Ganjali MR, Maragheh MG. Electrochemical fabrication of praseodymium cations doped iron oxide nanoparticles with enhanced charge storage and magnetic capabilities. Journal of Materials Science: Materials in Electronics. 2017;29(6):5163-72.

16. Aghazadeh M, Karimzadeh I, Ganjali MR. Improvement of supercapacitive and superparamagnetic capabilities of iron oxide through electrochemically grown La3+ doped Fe3O4 nanoparticles. Journal of Materials Science: Materials in Electronics. 2017;28(24):19061-70.

[17] M. Aghazadeh, I. Karimzadeh, and M.R. Ganjali, Enhancing the Supercapacitive and Superparamagnetic Performances of Iron Oxide Nanoparticles through Yttrium Cations Electro-chemical Doping, Mater. Res. 21(5), e20180094 (2018). doi: 10.1590/1980-5373-mr-2018-0094.

18. Li G-R, Xu H, Lu X-F, Feng J-X, Tong Y-X, Su C-Y. Electrochemical synthesis of nanostructured materials for electrochemical energy conversion and storage. Nanoscale. 2013;5(10):4056.

19. Aghazadeh M, Malek Barmi A-A, Mohammad Shiri H, Sedaghat S. Cathodic electrodeposition of Y(OH)3 and Y2O3 nanostructures from chloride bath. Part II: Effect of the bath temperature on the crystal structure, composition and morphology. Ceramics International. 2013;39(2):1045-55.

20. Aghazadeh M, Karimzadeh I, Ganjali MR. Preparation of Nano-sized Bismuth-Doped Fe3O4 as an Excellent Magnetic Material for Supercapacitor Electrodes. Journal of Electronic Materials. 2018;47(5):3026-36.

21. Guerrini L, Alvarez-Puebla R, Pazos-Perez N. Surface Modifications of Nanoparticles for Stability in Biological Fluids. Materials. 2018;11(7):1154.

22. Karimzadeh I, Dizaji HR, Aghazadeh M. Preparation, characterization and PEGylation of superparamagnetic Fe3O4nanoparticles from ethanol medium via cathodic electrochemical deposition (CED) method. Materials Research Express. 2016;3(9):095022.

23. Tran PA, Nguyen HT, Fox K, Tran N. In vitro cytotoxicity of iron oxide nanoparticles: effects of chitosan and polyvinyl alcohol as stabilizing agents. Materials Research Express. 2018;5(3):035051.

24. Aghazadeh M. One-step cathodic electrosynthesis of surface capped Fe 3 O 4 ultra-fine nanoparticles from ethanol medium without using coating agent. Materials Letters. 2018;211:225-9.

25. Sanchez LM, Martin DA, Alvarez VA, Gonzalez JS. Polyacrylic acid-coated iron oxide magnetic nanoparticles: The polymer molecular weight influence. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2018;543:28-37.

26. Karimzadeh I, Aghazadeh M, Doroudi T, Ganjali M, Kolivand P. Effective Preparation, Characterization and In Situ Surface Coating of Superparamagnetic Fe3O4 Nanoparticles with Polyethyleneimine Through Cathodic Electrochemical Deposition (CED). Current Nanoscience. 2017;13(2):167-74.

27. Osial M, Rybicka P, Pękała M, Cichowicz G, Cyrański M, Krysiński P. Easy Synthesis and Characterization of Holmium-Doped SPIONs. Nanomaterials. 2018;8(6):430.

28. Park JC, Lee GT, Kim H-K, Sung B, Lee Y, Kim M, et al. Surface Design of Eu-Doped Iron Oxide Nanoparticles for Tuning the Magnetic Relaxivity. ACS Applied Materials & Interfaces. 2018;10(30):25080-9.

29. Aghazadeh M, Barmi A-AM, Hosseinifard M. Nanoparticulates Zr(OH)4 and ZrO2 prepared by low-temperature cathodic electrodeposition. Materials Letters. 2012;73:28-31.

30. Aghazadeh M, Ghaemi M, Golikand AN, Ahmadi A. Porous network of Y2O3 nanorods prepared by electrogeneration of base in chloride medium. Materials Letters. 2011;65(15-16):2545-8.

31. Aghazadeh M, Ghannadi Maragheh M, Ganjali MR, Norouzi P. Preparation and characterization of Mn5O8 nanoparticles: A novel and facile pulse cathodic electrodeposition followed by heat treatment. Inorganic and Nano-Metal Chemistry. 2017;47(7):1085-9.

32. Aghazadeh M. Synthesis, characterization, and study of the supercapacitive performance of NiO nanoplates prepared by the cathodic electrochemical deposition-heat treatment (CED-HT) method. Journal of Materials Science: Materials in Electronics. 2016;28(3):3108-17.

33. Aghazadeh M, Dalvand S. Large-Scale and Facile Electrochemical Preparation of β-Co(OH)2Nanocapsules and Investigation of their Supercapacitive Performance. Journal of The Electrochemical Society. 2013;161(1):D18-D25.

34. Wang J, Zhang B, Wang L, Wang M, Gao F. One-pot synthesis of water-soluble superparamagnetic iron oxide nanoparticles and their MRI contrast effects in the mouse brains. Materials Science and Engineering: C. 2015;48:416-23.

35. Huang Y, Keller AA. EDTA functionalized magnetic nanoparticle sorbents for cadmium and lead contaminated water treatment. Water Research. 2015;80:159-68.

36. Aghazadeh M, Karimzadeh I. One-pot Electro-synthesis and Characterization of Chitosan Capped Superparamagnetic Iron Oxide Nanoparticles (SPIONs) from Ethanol Media. Current Nanoscience. 2017;14(1).

37. Liu Y, Chen M, Yongmei H. Study on the adsorption of Cu(II) by EDTA functionalized Fe3O4 magnetic nano-particles. Chemical Engineering Journal. 2013;218:46-54.

38. Ghasemi E, Heydari A, Sillanpää M. Superparamagnetic Fe3O4@EDTA nanoparticles as an efficient adsorbent for simultaneous removal of Ag(I), Hg(II), Mn(II), Zn(II), Pb(II) and Cd(II) from water and soil environmental samples. Microchemical Journal. 2017;131:51-6.

39. Bajpai AK, Gupta R. Synthesis and characterization of magnetite (Fe3O4)-Polyvinyl alcohol-based nanocomposites and study of superparamagnetism. Polymer Composites. 2009:NA-NA.

40. Aghazadeh M, Karimzadeh I, Ganjali MR. Preparation and Characterization of Amine- and Carboxylic Acid-functionalized Superparamagnetic Iron Oxide Nanoparticles Through a One-step Facile Electrosynthesis Method. Current Nanoscience. 2018;15(2):169-77.

41. Aghazadeh M, Karimzadeh I, Ganjali MR. PVP capped Mn 2+ doped Fe 3 O 4 nanoparticles: A novel preparation method, surface engineering and characterization. Materials Letters. 2018;228:137-40.

42. Mahmoudi M, Simchi A, Imani M, Milani AS, Stroeve P. Optimal Design and Characterization of Superparamagnetic Iron Oxide Nanoparticles Coated with Polyvinyl Alcohol for Targeted Delivery and Imaging†. The Journal of Physical Chemistry B. 2008;112(46):14470-81.

43. Sanaeifar N, Rabiee M, Abdolrahim M, Tahriri M, Vashaee D, Tayebi L. A novel electrochemical biosensor based on Fe 3 O 4 nanoparticles-polyvinyl alcohol composite for sensitive detection of glucose. Analytical Biochemistry. 2017;519:19-26.

44. Durmus Z, Erdemi H, Aslan A, Toprak MS, Sozeri H, Baykal A. Synthesis and characterization of poly(vinyl phosphonic acid) (PVPA)–Fe3O4 nanocomposite. Polyhedron. 2011;30(2):419-26.

45. Shete PB, Patil RM, Tiwale BM, Pawar SH. Water dispersible oleic acid-coated Fe3O4 nanoparticles for biomedical applications. Journal of Magnetism and Magnetic Materials. 2015;377:406-10.

46. Li Q, Kartikowati CW, Horie S, Ogi T, Iwaki T, Okuyama K. Correlation between particle size/domain structure and magnetic properties of highly crystalline Fe3O4 nanoparticles. Scientific Reports. 2017;7(1).

[47] M. Aghazadeh and I. Karimzadeh, One-step Cathodic Electrochemical Synthesis and Characterization of Dextran Coated Magnetite Nanoparticles, J. Nanoanal. 4(3), 228-238 (2017). doi: 10.22034/JNA.2017.539366.