Herein, by studying a stepwise phase transformation of 23 nm FeO-Fe3O4 core-shell nanocubes into Fe3O4, we identify a composition at which the magnetic heating performance of the nanocubes is not affected by the medium viscosity and aggregation. Structural and magnetic characterizations reveal the transformation of the FeO-Fe3O4 nanocubes from having stoichiometric phase compositions into Fe 2+ deficient Fe3O4 phases. The resultant nanocubes contain tiny compressed and randomly distributed FeO sub-domains as well as structural defects. This phase transformation causes a tenfold increase in the magnetic losses of the nanocubes, which remains exceptionally insensitive to the medium viscosity as well as aggregation unlike similarly sized single-phase magnetite nanocubes. We observe that the dominant relaxation mechanism switches from Néel in fresh core-shell nanocubes to Brownian in partially oxidized nanocubes and once again to Néel in completely treated nanocubes. The Fe 2+ deficiencies and structural defects appear to reduce the magnetic energy barrier and anisotropy field, thereby driving the overall relaxation into Néel process. The magnetic losses of the particles remain unchanged through a progressive internalization/association to ovarian cancer cells. Moreover, the particles induce a significant cell death after being exposed to hyperthermia treatment. Here, we present the largest heating performance that has been reported to date for 23 nm iron oxide nanoparticles under cellular and intracellular conditions. Our findings clearly demonstrate the positive impacts of the Fe 2+ deficiencies and structural defects in the Fe3O4 structure on the heating performance under cellular and intracellular conditions.
Nanoparticle‐based magnetic hyperthermia is a well‐known thermal therapy platform studied to treat solid tumors, but its use for monotherapy is limited due to incomplete tumor eradication at hyperthermia temperature (45 °C). It is often combined with chemotherapy for obtaining a more effective therapeutic outcome. Cubic‐shaped cobalt ferrite nanoparticles (Co–Fe NCs) serve as magnetic hyperthermia agents and as a cytotoxic agent due to the known cobalt ion toxicity, allowing the achievement of both heat and cytotoxic effects from a single platform. In addition to this advantage, Co–Fe NCs have the unique ability to form growing chains under an alternating magnetic field (AMF). This unique chain formation, along with the mild hyperthermia and intrinsic cobalt toxicity, leads to complete tumor regression and improved overall survival in an in vivo murine xenograft model, all under clinically approved AMF conditions. Numerical calculations identify magnetic anisotropy as the main Co–Fe NCs’ feature to generate such chain formations. This novel combination therapy can improve the effects of magnetic hyperthermia, inaugurating investigation of mechanical behaviors of nanoparticles under AMF, as a new avenue for cancer therapy.
Solution processing
of highly performing photonic crystals has
been a towering ambition for making them technologically relevant
in applications requiring mass and large-area production. It would
indeed represent a paradigm changer for the fabrication of sensors
and for light management nanostructures meant for photonics and advanced
photocatalytic systems. On the other hand, solution-processed structures
often suffer from low dielectric contrast and poor optical quality
or require complex deposition procedures due to the intrinsic properties
of components treatable from solution. This work reports on a low-temperature
sol–gel route between the alkoxides of Si and Ti and poly(acrylic
acid), leading to stable polymer–inorganic hybrid materials
with tunable refractive index and, in the case of titania hybrid,
photoactive properties. Alternating thin films of the two hybrids
allows planar photonic crystals with high optical quality and dielectric
contrast as large as 0.64. Moreover, low-temperature treatments also
allow coupling the titania hybrids with several temperature-sensitive
materials including dielectric and semiconducting polymers to fabricate
photonic structures. These findings open new perspectives in several
fields; preliminary results demonstrate that the hybrid structures
are suitable for sensing and the enhancement of the catalytic activity
of photoactive media and light emission control.
Here, the synthesis and proof of exploitation of three‐material inorganic heterostructures made of iron oxide‐gold‐copper sulfide (Fe3O4@Au@Cu2−xS) are reported. Starting with Fe3O4‐Au dumbbell heterostructure as seeds, a third Cu2−xS domain is selectively grown on the Au domain. The as‐synthesized trimers are transferred to water by a two‐step ligand exchange procedure exploiting thiol‐polyethylene glycol to coordinate Au and Cu2−xS surfaces and polycatechol–polyethylene glycol to bind the Fe3O4 surface. The saline stable trimers possess multi‐functional properties: the Fe3O4 domain, of appropriate size and crystallinity, guarantees optimal heating losses in magnetic hyperthermia (MHT) under magnetic field conditions of clinical use. These trimers have indeed record values of specific adsorption rate among the inorganic‐heterostructures so far reported. The presence of Au and Cu2−xS domains ensures a large adsorption which falls in the first near‐infrared (NIR) biological window and is here exploited, under laser excitation at 808 nm, to produce photo‐thermal heat alone or in combination with MHT obtained from the Fe3O4 domain. Finally, an intercalation protocol with radioactive 64Cu ions is developed on the Cu2−xS domain, reaching high radiochemical yield and specific activity making the Fe3O4@Au@Cu2−xS trimers suitable as carriers for 64Cu in internal radiotherapy (iRT) and traceable by positron emission tomography (PET).
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