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Size-Controlled Bimagnetic FePt/iron oxide Hybrid Nanocrystals: One-Pot
Synthesis, Structural-Magnetic Characterization and Potential
Applications as MRI Contrast Agents
Albert Figuerola,a Angela Fiore,a Teresa Pellegrino,a Riccardo Di Corato,a Andrea Falqui,b
Cinzia Giannini,c Edoardo Micotti,d Alessandro Lascialfari,e Maurizio Corti,d Roberto
Cingolani,a Davide Cozzoli,a Liberato Mannaa
a
National Nanotechnology Laboratory of CNR Distretto Tecnologico ISUFI, Lecce-ITALY;
Institut National de Sciences Appliqueés – INSA Departement de Genie Physique, Toulouse
Cedex 4, FRANCE; cCNR-Istituto di Cristallografia, Bari, ITALY; dDip. di Fisica “A.Volta”,
Università di Pavia, and Unita’ CNR-INFM and CNISM, Pavia, ITALY; eIstituto di
Fisiologia Generale e Chimica Biologica "G. Esposito", Milano and S3-CNR-INFM ,
Modena, ITALY.
b
Developments in wet-chemical approaches to inorganic nanostructures have opened access to
finely size and shape controlled nanocrystals (NCs) of a variety of semiconductor, metal and
magnetic materials. Considerable advances in the preparation of structurally complex NCs in
liquid media have been recently devised with the synthesis of first prototypes of colloidal
hybrid nanocrystals (HNCs), in which multiple material domains are assembled together in a
unique particle via epitaxial interfaces [1]. The ability to control the topological distribution
in terms of chemical nature in colloidal nanoheterostructures is among the most challenging
goals of current nanochemistry research. HNCs hold promise as novel generations of
revolutionary nanoscale building blocks, to which the coexistence of different chemicalphysical properties (e.g., luminescence, magnetism, and catalytic activity) naturally attributes
multifunctionality and unprecedented chemical-physical behavior, as compared to that
exhibited by the individual components alone [2-5].
In this contribution, we present a step further in this field, demonstrating a facile one-pot
approach of a novel type of noncentrosymmetric bimagnetic HNCs with tailorable geometric
parameters. We show seedless, surfactant-assisted synthesis to prepare dimer-like HNCs,
individually comprising one “hard” FePt and one “soft” iron oxide magnetic section, both of
which are size-tunable in the 3-20 nm range. Our strategy allows one to control the nucleation
and growth stages for each material domain separately by temperature-programmed heating
of a suitable mixture containing all the necessary molecular precursors and organic
stabilizers. The influence of various reaction parameters on the structural-compositional
features of the final FePt/iron oxide heterodimers, such as the relative reactant to ligand
molar ratio, their absolute concentrations, and the temperature modulation, has been
examined in detail by a combination of powder XRD Diffraction measurements, ICP
elemental analyses, and Low and High Resolution TEM investigations.
The size-related magnetic properties of the HNCs and the involved magnetic exchange
coupling have been disclosed by temperature and field-dependent measurements with a
SQUID magnetometer. The control over the absolute and relative sizes of the two materials
in the heterostructure allows the synthesis of several nanosystems with a wide rage of
magnetic properties.
The 4th International Congress of Nanotechnology
Topic Area: Nanomaterials
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Superparamagnetic nanoparticles suspensions, also known as ferrofluids, have been shown to
be useful as multifunctional tools in biomedical applications.[6] Both diagnosis and
therapeutic functions can be achieved due to the magnetic response of the ferrofluid during its
exposure to an external magnetic field. Their main advantages are the absence of residual
magnetization in the fluid after the removal of the field, avoiding possible undesired tissue
damages or nanoparticles aggregation, and the potential magnetic addressing of the ferrofluid
to a specific tissue that would allow injection of minor doses of either inorganic material
and/or chemotherapeutic drugs and would simultaneously decrease further collateral effects
in healthy tissues. In order to check the potential of FePt/iron oxide nanocrystals as image
contrast agents in Magnetic Resonance Imaging (MRI), NMR-Dispersion measurements have
been performed on previously water-transferred FePt nanocrystals and on the corresponding
FePt/iron oxide heterostructures. The data confirm that some FePt/iron oxide hybrid materials
show higher relaxivity values with respect to the clinically used ENDOREM compound,[7]
which indicates their high potential as imaging contrast agents.
References:
[1] P. Davide Cozzoli, Teresa Pellegrino, Liberato Manna, Chem. Soc. Rev., 35 (2006) 1195.
[2] Hyungrak Kim, Marc Achermann, Laurent P. Balet, Jennifer A. Hollingsworth, Victor I.
Klimov, J. Am. Chem. Soc., 127 (2005) 544.
[3] Marianna Casavola, Vicenzo Grillo, Elvio Carlino, Cinzia Giannini, Fabia Gozzo,
Enrique Fernandez Pinel, Miguel Angel Garcia, Liberato Manna, Roberto Cingolani, P.
Davide Cozzoli, Nano Lett., 7 (2007) 1386.
[4] Hao Zeng, Jing Li, Z. L. Wang, J. P. Liu, Shouheng Sun, Nano Lett., 4 (2004) 187.
[5] Teresa Pellegrino, Angela Fiore, Elvio Carlino, Cinzia Giannini, P. Davide Cozzoli,
Giuseppe Ciccarella, Marc Respaud, Luca Palmirotta, Roberto Cingolani, Liberato Manna, J.
Am. Chem. Soc., 128 (2006) 6690.
[6] Venkatasubramaniam S. Kalambur, Bumsoo Han, Bruce E. Hammer, Thomas W. Shield,
John C. Bischof, Nanotech., 16 (2005) 1221.
[7] Yi-Xiang J.Wang; Shahid M. Hussain; Gabriel P. Krestin, Eur. Radiol. 2001, 11, 2319.
Figure:
The 4th International Congress of Nanotechnology
Topic Area: Nanomaterials