Magnetic hyperthermia (MHT) exploits magnetic nanoparticles (MNPs) to burn solid tumors. Here, we overview promising MNPs and magnetic assemblies used in MHT alone or in combination with chemotherapy, radiotherapy, immunotherapy or phototherapy.
The assembly of magnetic cores into regular structures may notably influence the properties displayed by a magnetic colloid. Here, key synthesis parameters driving the self‐assembly process capable of organizing colloidal magnetic cores into highly regular and reproducible multi‐core nanoparticles are determined. In addition, a self‐consistent picture that explains the collective magnetic properties exhibited by these complex assemblies is achieved through structural, colloidal, and magnetic means. For this purpose, different strategies to obtain flower‐shaped iron oxide assemblies in the size range 25–100 nm are examined. The routes are based on the partial oxidation of Fe(OH)2, polyol‐mediated synthesis or the reduction of iron acetylacetonate. The nanoparticles are functionalized either with dextran, citric acid, or alternatively embedded in polystyrene and their long‐term stability is assessed. The core size is measured, calculated, and modeled using both structural and magnetic means, while the Debye model and multi‐core extended model are used to study interparticle interactions. This is the first step toward standardized protocols of synthesis and characterization of flower‐shaped nanoparticles.
Magnetic nanoparticles are being
developed as structural and functional
materials for use in diverse areas, including biomedical applications.
Here, we report the synthesis of maghemite (γ-Fe
2
O
3
) nanoparticles with distinct morphologies: single-core
and multicore, including hollow spheres and nanoflowers, prepared
by the polyol process. We have used sodium acetate to control the
nucleation and assembly process to obtain the different particle morphologies.
Moreover, from samples obtained at different time steps during the
synthesis, we have elucidated the formation mechanism of the nanoflowers:
the initial phases of the reaction present a lepidocrocite (γ-FeOOH)
structure, which suffers a fast dehydroxylation, transforming to an
intermediate “undescribed” phase, possibly a partly
dehydroxylated lepidocrocite, which after some incubation time evolves
to maghemite nanoflowers. Once the nanoflowers have been formed, a
crystallization process takes place, where the γ-Fe
2
O
3
crystallites within the nanoflowers grow in size (from
∼11 to 23 nm), but the particle size of the flower remains
essentially unchanged (∼60 nm). Samples with different morphologies
were coated with citric acid and their heating capacity in an alternating
magnetic field was evaluated. We observe that nanoflowers with large
cores (23 nm, controlled by annealing) densely packed (tuned by low
NaAc concentration) offer 5 times enhanced heating capacity compared
to that of the nanoflowers with smaller core sizes (15 nm), 4 times
enhanced heating effect compared to that of the hollow spheres, and
1.5 times enhanced heating effect compared to that of single-core
nanoparticles (36 nm) used in this work.
The use of magnetic nanoparticles (MNPs) to locally increase the temperature at the nanoscale under the remote application of alternating magnetic fields (magnetic particle hyperthermia, MHT) has become an important...
Here, we resolve the nature of the moment coupling between 10-nm DMSA-coated magnetic nanoparticles. The individual iron oxide cores were composed of > 95 % maghemite and agglomerated to clusters. At room temperature the ensemble behaved as a superparamagnet according to Mössbauer and magnetization measurements, however, with clear signs of dipolar interactions. Analysis of temperature-dependent AC susceptibility data in the superparamagnetic regime indicates a tendency for dipolar coupled anticorrelations of the core moments within the clusters. To resolve the directional correlations between the particle moments we performed polarized small-angle neutron scattering and determined the magnetic spin-flip cross-section of the powder in low magnetic field at 300 K. We extract the underlying magnetic correlation function of the magnetization vector field by an indirect Fourier transform of the cross-section. The correlation function suggests non-stochastic preferential alignment between neighboring moments despite thermal fluctuations, with anticorrelations clearly dominating for next-nearest moments. These tendencies are confirmed by Monte Carlo simulations of such core-clusters.
The design of magnetic nanostructures whose magnetic heating efficiency remains unaffected at the tumor site is a fundamental requirement to further advance magnetic hyperthermia in clinic. This work demonstrates that the confinement of magnetic nanoparticles (NPs) into a submicrometric cavity is a key strategy to enable a certain degree of nanoparticle motion and minimize aggregation effects, consequently preserving the magnetic heat loss of iron oxide nanocubes (IONCs) under different conditions, including intracellular environments. We fabricated magnetic Layer-by-Layer (LbL) self-assembled polyelectrolyte submicrometric capsules using three different approaches, and we studied their heating efficiency as obtained in aqueous dispersions and once internalized by tumor cells. First, IONCs were added to the hollow cavities of LbL submicrocapsules, allowing the IONCs to move to a certain extent in the capsule cavities.Second, IONCs were co-encapsulated into solid calcium carbonate cores coated with LbL polymer shells.Third, IONCs were incorporated within the polymer layers of the LbL capsule walls. In aqueous solution, the higher specific absorption rate (SAR) values were related to the ones of free IONCs, while lower SAR values were recorded for capsule/core assemblies. However, after uptake by cancer cell lines (SKOV-3 cells), the SAR values of the free IONCs were significantly lower than those observed for capsule/core assemblies, especially after prolonged incubation periods (24 and 48 hours). These results show that IONCs packed into submicrocavities preserve the magnetic losses, as SAR values remained almost invariable. Conversely, free IONCs without the protective capsule shell agglomerated and their magnetic losses are strongly reduced. Indeed, IONC loaded capsules and free IONCs reside inside endosomal and lysosomal compartments after cellular uptake, show magnetic losses strongly reduced due to the immobilization and aggregation in centrosymmetrical structures in the intracellular vesicles. The confinement of IONCs into submicrometric cavities is a key strategy to provide a sustained and predictable heating dose inside biological matrices.
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