Cobalt ferrite nanoparticles (CoFe2O4 NPs) were synthesized by coprecipitation followed by treatments with diluted nitric acid and sodium citrate. Transmission electron microscope (TEM) and photon correlation spectroscopy (PCS) characterization showed that the size distributions of these nanoparticles were monodisperse and that no aggregation occurred. This colloid showed a long-term stability. Through adjustment of the concentrations of reactants and reaction temperature, the size of the NPs can be tuned from 6 to 80?nm. The size-control mechanism is explained by a nucleation-growth model, where the local concentration of monomers is assumed to decide the size of nuclei, and reaction temperatures influence the growth of nuclei. Magnetization and relaxivity measurements showed that the NPs revealed size-dependent magnetization and relaxivity properties, which are explained via a “dead magnetic layer” theory where reductions of saturation magnetization ( ) and are assumed to be caused by the demagnetization of surface spins. 1. Introduction The development of uniform magnetic nanoparticles (MNPs) has been intensively pursued for their scientific and technological importance [1–3]. The synthesis of MNPs with average sizes from 2 to 50?nm is of significant importance because of their applications in several fields, especially in biomedicine for magnetic resonance imaging (MRI) [4, 5], cell labelling [6, 7], and drug delivery [8–11]. Of special interest are their magnetic properties in which the differences between a massive or bulk material and a nanoscaled one are especially pronounced. The magnetic properties are particularly sensitive to the particle size, which is determined by the finite size effects (related to the reduced number of spins cooperatively linked within the particle), and by surface effects (greater as the particle size decreases) [12–15]. The water solubility of MNPs is necessary for medical applications, and their aggregation, caused by the huge specific surface area and magnetic interactions, must be avoided. It is thus necessary to adopt methods to stabilize the MNPs, either by using surfactants or by changing their surface potential. Oleic acid and oleylamine are the surfactants most used for the synthesis of MNPs in organic solvent [16–19] and citric acid for water phase synthesis [20–23], as these capping agents tend to be absorbed on the particular high-energy facets. Their overall specific surface energy is more or less reduced, so the tendency towards aggregation is decreased. The ratio between growth rates in different
References
[1]
S. A. Majetich and Y. Jin, “Magnetization directions of individual nanoparticles,” Science, vol. 284, no. 5413, pp. 470–473, 1999.
[2]
H. Zeng, J. Li, J. P. Liu, Z. L. Wang, and S. Sun, “Exchange-coupled nanocomposite magnets by nanoparticle self-assembly,” Nature, vol. 420, no. 6914, pp. 395–398, 2002.
[3]
C. Thirion, W. Wernsdorfer, and D. Mailly, “Switching of magnetization by nonlinear resonance studied in single nanoparticles,” Nature Materials, vol. 2, no. 8, pp. 524–527, 2003.
[4]
S. Laurent, D. Forge, M. Port et al., “Magnetic iron oxide nanoparticles: synthesis, stabilization, vectorization, physicochemical characterizations and biological applications,” Chemical Reviews, vol. 108, no. 6, pp. 2064–2110, 2008.
[5]
L. Schr?der, T. J. Lowery, C. Hilty, D. E. Wemmer, and A. Pines, “Molecular imaging using a targeted magnetic resonance hyperpolarized biosensor,” Science, vol. 314, no. 5798, pp. 446–449, 2006.
[6]
S. Laurent, S. Boutry, I. Mahieu, L. Vander Elst, and R. N. Muller, “Iron oxide based MR contrast agents: from chemistry to cell labeling,” Current Medicinal Chemistry, vol. 16, no. 35, pp. 4712–4727, 2009.
[7]
B. P. Barnett, A. Arepally, P. V. Karmarkar et al., “Magnetic resonance-guided, real-time targeted delivery and imaging of magnetocapsules immunoprotecting pancreatic islet cells,” Nature Medicine, vol. 13, no. 8, pp. 986–991, 2007.
[8]
M. Mahmoudi, S. Sant, B. Wang, S. Laurent, and T. Sen, “Superparamagnetic iron oxide nanoparticles (SPIONs): development, surface modification and applications in chemotherapy,” Advanced Drug Delivery Reviews, vol. 63, no. 1-2, pp. 24–46, 2011.
[9]
S. J. Son, J. Reichel, B. He, M. Schuchman, and S. B. Lee, “Magnetic nanotubes for magnetic-field-assisted bioseparation, biointeraction, and drug delivery,” Journal of the American Chemical Society, vol. 127, no. 20, pp. 7316–7317, 2005.
[10]
Q. Cao, X. Han, and L. Li, “Enhancement of the efficiency of magnetic targeting for drug delivery: development and evaluation of magnet system,” Journal of Magnetism and Magnetic Materials, vol. 323, no. 15, pp. 1919–1924, 2011.
[11]
Y. Yoshida, S. Fukui, S. Fujimoto et al., “Ex vivo investigation of magnetically targeted drug delivery system,” Journal of Magnetism and Magnetic Materials, vol. 310, no. 2, pp. 2880–2882, 2007.
[12]
W. S. Seo, H. H. Jo, K. Lee, B. Kim, S. J. Oh, and J. T. Park, “Size-dependent magnetic properties of colloidal Mn3O4 and MnO nanoparticles,” Angewandte Chemie: International Edition, vol. 43, no. 9, pp. 1115–1117, 2004.
[13]
T.-J. Park, G. C. Papaefthymiou, A. J. Viescas, A. R. Moodenbaugh, and S. S. Wong, “Size-dependent magnetic properties of single-crystalline multiferroic BiFeO3 nanoparticles,” Nano Letters, vol. 7, no. 3, pp. 766–772, 2007.
[14]
K. N. K. Kowlgi, G. J. M. Koper, S. J. Picken, U. Lafont, L. Zhang, and B. Norder, “Synthesis of magnetic noble metal (nano)particles,” Langmuir, vol. 27, no. 12, pp. 7783–7787, 2011.
[15]
H. Duan, M. Kuang, X. Wang, Y. A. Wang, H. Mao, and S. Nie, “Reexamining the effects of particle size and surface chemistry on the magnetic properties of iron oxide nanocrystals: new insights into spin disorder and proton relaxivity,” The Journal of Physical Chemistry C, vol. 112, no. 22, pp. 8127–8131, 2008.
[16]
S. Sun, H. Zeng, D. B. Robinson et al., “Monodisperse MFe2O4 (M = Fe, Co, Mn) Nanoparticles,” Journal of the American Chemical Society, vol. 126, no. 1, pp. 273–279, 2004.
[17]
K. T. Wu, Y. D. Yao, and H. K. Huang, “Comparison of dynamic and optical properties of Fe3O4 ferrofluid emulsion in water and oleic acid under magnetic field,” Journal of Magnetism and Magnetic Materials, vol. 209, no. 1-3, pp. 246–248, 2000.
[18]
Z. Jia, J. W. Harrell, and R. D. K. Misra, “Synthesis and magnetic properties of self-assembled FeRh nanoparticles,” Applied Physics Letters, vol. 93, no. 2, Article ID 022504, 2008.
[19]
G. K. Das, B. C. Heng, S.-C. Ng et al., “Gadolinium oxide ultranarrow nanorods as multimodal contrast agents for optical and magnetic resonance imaging,” Langmuir, vol. 26, no. 11, pp. 8959–8965, 2010.
[20]
Y. Sahoo, A. Goodarzi, M. T. Swihart et al., “Aqueous ferrofluid of magnetite nanoparticles: fluorescence labeling and magnetophoretic control,” The Journal of Physical Chemistry B, vol. 109, no. 9, pp. 3879–3885, 2005.
[21]
M. Rǎcuciu, D. E. Creang?, and A. Airinei, “Citric-acid-coated magnetite nanoparticles for biological applications,” European Physical Journal E, vol. 21, no. 2, pp. 117–121, 2006.
[22]
D. E. Creang?, M. Culea, C. N?dejde, S. Oancea, L. Curecheriu, and M. Racuciu, “Magnetic nanoparticle effects on the red blood cells,” Journal of Physics: Conference Series, vol. 170, no. 1, Article ID 012019, 2009.
[23]
T. Goetze, C. Gansau, N. Buske, M. Roeder, P. G?rnert, and M. Bahr, “Biocompatible magnetic core/shell nanoparticles,” Journal of Magnetism and Magnetic Materials, vol. 252, no. 1-3, pp. 399–402, 2002.
[24]
A. Villanueva, M. Canete, A. G. Roca, et al., “The influence of surface functionalization on the enhanced internalization of magnetic nanoparticles in cancer cells,” Nanotechnology, vol. 20, no. 11, Article ID 115103, 2009.
[25]
R. Massart, “Preparation of aqueous magnetic liquids in alkaline and acidic media,” IEEE Transactions on Magnetics, vol. 17, no. 2, pp. 1247–1248, 1981.
[26]
F. A. Tourinho, R. Franck, and R. Massart, “Aqueous ferrofluids based on manganese and cobalt ferrites,” Journal of Materials Science, vol. 25, no. 7, pp. 3249–3254, 1990.
[27]
J.-C. Bacri, R. Perzynski, D. Salin, V. Cabuil, and R. Massart, “Ionic ferrofluids: a crossing of chemistry and physics,” Journal of Magnetism and Magnetic Materials, vol. 85, no. 1-3, pp. 27–32, 1990.
[28]
J. F. Hochepied, P. Bonville, and M. P. Pileni, “Nonstoichiometric zinc ferrite nanocrystals: syntheses and unusual magnetic properties,” The Journal of Physical Chemistry B, vol. 104, no. 5, pp. 905–912, 2000.
[29]
V. F. Puntes, K. M. Krishnan, and A. P. Alivisatos, “Colloidal nanocrystal shape and size control: the case of cobalt,” Science, vol. 291, no. 5511, pp. 2115–2117, 2001.
[30]
G. A. Sawatzky, J. M. D. Coey, and A. H. Morrish, “M?ssbauer study of electron hopping in the octahedral sites of Fe3O4,” Journal of Applied Physics, vol. 40, no. 3, pp. 1402–1403, 1969.
[31]
G. A. Sawatzky, F. van der Woude, and A. H. Morrish, “M?ssbauer study of several ferrimagnetic spinels,” Physical Review, vol. 187, no. 2, pp. 747–757, 1969.
[32]
A. N. Zakharov, E. A. Gan'shina, N. S. Perov, N. I. Yurasov, and A. Y. Shenkarenko, “Opal photonic crystals modified by Fe-based inclusions,” Inorganic Materials, vol. 41, no. 11, pp. 1185–1188, 2005.
[33]
R. Grau-Crespo, A. Y. Al-Baitai, I. Saadoune, and N. H. De Leeuw, “Vacancy ordering and electronic structure of γ-Fe2O3 (maghemite): a theoretical investigation,” Journal of Physics Condensed Matter, vol. 22, no. 25, Article ID 255401, 2010.
[34]
K. J. Davies, S. Wells, R. V. Upadhyay et al., “The observation of multi-axial anisotropy in ultrafine cobalt ferrite particles used in magnetic fluids,” Journal of Magnetism and Magnetic Materials, vol. 149, no. 1-2, pp. 14–18, 1995.
[35]
N. Moume, P. Bonville, and M. P. Pileni, “Control of the size of cobalt ferrite magnetic fluids: M?ssbauer spectroscopy,” The Journal of Physical Chemistry, vol. 100, no. 34, pp. 14410–14416, 1996.
[36]
L. Josephson, J. Lewis, P. Jacobs, P. F. Hahn, and D. D. Stark, “The effects of iron oxides on proton relaxivity,” Magnetic Resonance Imaging, vol. 6, no. 6, pp. 647–653, 1988.
[37]
T. Allkemper, C. Bremer, L. Matuszewski, W. Ebert, and P. Reimer, “Contrast-enhanced blood-pool MR angiography with optimized iron oxides: effect of size and dose on vascular contrast enhancement in rabbits,” Radiology, vol. 223, no. 2, pp. 432–438, 2002.
[38]
S. Gangopadhyay, G. C. Hadjipanayis, B. Dale et al., “Magnetic properties of ultrafine iron particles,” Physical Review B, vol. 45, no. 17, pp. 9778–9787, 1992.
[39]
J. Aizenberg, A. J. Black, and G. M. Whitesides, “Control of crystal nucleation by patterned self-assembled monolayers,” Nature, vol. 398, no. 6727, pp. 495–498, 1999.
[40]
S.-M. Lee, Y.-W. Jun, S.-N. Cho, and J. Cheon, “Single-crystalline star-shaped nanocrystals and their evolution: programming the geometry of nano-building blocks,” Journal of the American Chemical Society, vol. 124, no. 38, pp. 11244–11245, 2002.
[41]
X. Huang and Z. Chen, “Preparation of CoFe2O4/SiO2 nanocomposites by sol-gel method,” Journal of Crystal Growth, vol. 271, no. 1-2, pp. 287–293, 2004.
[42]
J. Li, D. Dai, B. Zhao, Y. Lin, and C. Liu, “Properties of ferrofluid nanoparticles prepared by coprecipitation and acid treatment,” Journal of Nanoparticle Research, vol. 4, no. 3, pp. 261–264, 2002.
[43]
J. Araújo, E. Vega, C. Lopes, M. A. Egea, M. L. Garcia, and E. B. Souto, “Effect of polymer viscosity on physicochemical properties and ocular tolerance of FB-loaded PLGA nanospheres,” Colloids and Surfaces B, vol. 72, no. 1, pp. 48–56, 2009.
[44]
H.-S. Kim, W.-I. Park, M. Kang, and H.-J. Jin, “Multiple light scattering measurement and stability analysis of aqueous carbon nanotube dispersions,” Journal of Physics and Chemistry of Solids, vol. 69, no. 5-6, pp. 1209–1212, 2008.
[45]
D. Desai, S. Kothari, and M. Huang, “Solid-state interaction of stearic acid with povidone and its effect on dissolution stability of capsules,” International Journal of Pharmaceutics, vol. 354, no. 1-2, pp. 77–81, 2008.
[46]
S. Ikeda, K. Miura, H. Yamamoto et al., “A perpendicular-anisotropy CoFeB-MgO magnetic tunnel junction,” Nature Materials, vol. 9, no. 9, pp. 721–724, 2010.
[47]
P. Gillis, F. Moiny, and R. A. Brooks, “On T2-shortening by strongly magnetized spheres: a partial refocusing model,” Magnetic Resonance in Medicine, vol. 47, no. 2, pp. 257–263, 2002.
[48]
I. Prigogine and S. A. Rice, Advances in Chemical Physics, vol. 98, Wiley, New York, NY, USA, 1997.