Magnetite particles with an average size of 39 nm and good monodispersity have been synthesized by coprecipitation at 70 °C from ferrous Fe2+ and ferric Fe3+ ions by a (N(CH3)4OH) solution, followed by hydrothermal treatment at 250 °C. The magnetite nanoparticles before the hydrothermal step display an average size of 12 nm and are highly oxidized when they are in contact with air. Complementary microstructural and magnetic characterizations of nanoparticles after hydrothermal treatment show unambiguously that they consist of magnetite with only a slight deviation from stoichiometry (δ ≈ 0.05), leading to Fe2.95O4.

Hydrothermal synthesis of monodisperse magnetite nanoparticles

We present an innovative approach to the production of single-crystal iron oxide nanorings employing a solution-based route. Single-crystal hematite (alpha-Fe2O3) nanorings were synthesized using a double anion-assisted hydrothermal method (involving phosphate and sulfate ions), which can be divided into two stages: (1) formation of capsule-shaped alpha-Fe2O3 nanoparticles and (2) preferential dissolution along the long dimension of the elongated nanoparticles (the c axis of alpha-Fe2O3) to form nanorings. The shape of the nanorings is mainly regulated by the adsorption of phosphate ions on faces parallel to c axis of alpha-Fe2O3 during the nanocrystal growth, and the hollow structure is given by the preferential dissolution of the alpha-Fe2O3 along the c axis due to the strong coordination of the sulfate ions. By varying the ratios of phosphate and sulfate ions to ferric ions, we were able to control the size, morphology, and surface architecture to produce a variety of three-dimensional hollow nanostructures. These can then be converted to magnetite (Fe3O4) and maghemite (gamma-Fe2O3) by a reduction or reduction-oxidation process while preserving the same morphology. The structures and magnetic properties of these single-crystal alpha-Fe2O3, Fe3O4, and gamma-Fe2O3 nanorings were characterized by various analytical techniques. Employing off-axis electron holography, we observed the classical single-vortex magnetic state in the thin magnetite nanorings, while the thicker rings displayed an intriguing three-dimensional magnetic configuration. This work provides an easily scaled-up method for preparing tailor-made iron oxide nanorings that could meet the demands of a variety of applications ranging from medicine to magnetoelectronics.

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Large-scale synthesis of single-crystalline iron oxide magnetic nanorings.

A solid solution can exist of magnetite (Fe3O4) and maghemite (γ-Fe2O3), which is commonly referred to as nonstoichiometric or partially oxidized magnetite. The degree of stoichiometry in magnetite is quantitatively measured by determining the ratio of Fe2+ to Fe3+. Magnetite stoichiometry ( x = Fe2+/Fe3+) strongly influences several physical properties, including the coercitivity, sorption capacity, reduction potential, and crystalline structure. Magnetite stoichiometry has been extensively studied, although very little work exists examining the stoichiometry of nanoparticulate samples (<<100 nm); when the stoichiometry was measured for nanoparticulate samples, it was not validated with a secondary technique. Here, we review the three most common techniques to determine magnetite stoichiometry: (1) acidic dissolution; (2) Mossbauer spectroscopy; and (3) powder X-ray diffraction (pXRD), specifically with nanoparticulate samples in mind. Eight samples of nonstoichiometric magnetite were synthesized with x ranging from 0 to 0.50 and with the particle size kept as similar as possible (BET specific surface area = 63 ± 7 m2/g; particle size ≈ 20 nm). Our measurements indicate excellent agreement between stoichiometries determined from Mossbauer spectra and by acidic dissolution, suggesting that Mossbauer spectroscopy may be a useful means for estimating magnetite stoichiometry in nanoparticulate, multi-phases samples, such as those found in the environment. A significant linear correlation was also observed between the unit-cell length ( a ) of magnetite measured by pXRD and magnetite stoichiometry, indicating that pXRD may also be useful for determining particle stoichiometry, especially for mixed phased samples.

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Determination of nanoparticulate magnetite stoichiometry by Mössbauer spectroscopy, acidic dissolution, and powder X-ray diffraction: A critical review

Most studies on the synthesis of nanoparticles are currently focused on the controlled synthesis of new morphologies, including core-shell structures, which are expected to exhibit new magnetic pro...

Microstructural and Magnetic Investigations of Wüstite-Spinel Core-Shell Cubic-Shaped Nanoparticles

We observed Verwey transition in very small (6–14 nm) amine-coated octahedral magnetite (Fe3O4) nanoparticles that is not present in spherical similarly sized (4–13 nm) nanoparticles. Electron microscopy shows that octahedral nanoparticles have {111} facets with better cationic coordination symmetry as their surface. Spherical shape illustrates conventional superparamagnetic behavior; on the contrary, a characteristic Verwey transition near 120 K is prominent in field-cooled/zero-field-cooled curves of octahedral nanoparticles. Higher saturation magnetization in octahedral nanoparticles indicates lesser surface spin disorder and well-established anisotropy. Better surface coordination offers a reduced number of oxygen vacancies at the surface and, therefore, better stoichiometry results in a Verwey transition in octahedral nanoparticles. Electrical resistivity measurements show a sharp change in resistance for octahedral particles below the Verwey transition temperature which is completely hindered in sph...

Verwey Transition in Ultrasmall-Sized Octahedral Fe3O4 Nanoparticles

Canonical roles for macrophages in mediating the fibrotic response after a heart attack include extracellular matrix turnover and activation of cardiac fibroblasts to initiate collagen deposition. Here we reveal that macrophages directly contribute collagen to the forming post-injury scar. Unbiased transcriptomics shows an upregulation of collagens in both zebrafish and mouse macrophages following heart injury. Adoptive transfer of macrophages, from either collagen-tagged zebrafish or adult mouse GFPtpz-collagen donors, enhances scar formation via cell autonomous production of collagen. In zebrafish, the majority of tagged collagen localises proximal to the injury, within the overlying epicardial region, suggesting a possible distinction between macrophage-deposited collagen and that predominantly laid-down by myofibroblasts. Macrophage-specific targeting of col4a3bpa and cognate col4a1 in zebrafish significantly reduces scarring in cryoinjured hosts. Our findings contrast with the current model of scarring, whereby collagen deposition is exclusively attributed to myofibroblasts, and implicate macrophages as direct contributors to fibrosis during heart repair. Macrophages mediate the fibrotic response after a heart attack by extracellular matrix turnover and cardiac fibroblasts activation. Here the authors identify an evolutionarily-conserved function of macrophages that contributes directly to the forming post-injury scar through cell-autonomous deposition of collagen.

Macrophages directly contribute collagen to scar formation during zebrafish heart regeneration and mouse heart repair

Stoichiometric and cation-deficient magnetite Fe3−δO4 and γ-Fe2O3 particles have been prepared by the chemical method followed by heat treatments The magnetic and structural properties were studied using neutron diffraction, magnetic measurements, and Mossbauer spectroscopy Charge ordering of Fe3+ and Fe2+ and lattice distortion are not observed below the Verwey transition temperature in the stoichiometric and cation-deficient magnetite It is found that the lattice parameter and the Verwey transition temperature decrease as the cation vacancy increases The Verwey transition almost disappears in the Fe3−δO4 sample with δ=0066 Mossbauer spectra show that the ratio of Fe3+/Fe25+ in stoichiometric magnetite can be modified by heat treatment The Fe vacancies on the B sites change the nature of the Verwey transition No cation vacancy ordering is observed for γ-Fe2O3, due to the small amount of cation vacancies in the compound

Magnetic and structural studies of the Verwey transition in Fe3−δO4 nanoparticles

Epicardium-derived cells (EPDCs) contribute cardiovascular cell types during development and in adulthood respond to Thymosin β4 (Tβ4) and myocardial infarction (MI) by reactivating a fetal gene programme to promote neovascularization and cardiomyogenesis. The mechanism for epicardial gene (re-)activation remains elusive. Here we reveal that BRG1, the essential ATPase subunit of the SWI/SNF chromatin-remodelling complex, is required for expression of Wilms' tumour 1 (Wt1), fetal EPDC activation and subsequent differentiation into coronary smooth muscle, and restores Wt1 activity upon MI. BRG1 physically interacts with Tβ4 and is recruited by CCAAT/enhancer-binding protein β (C/EBPβ) to discrete regulatory elements in the Wt1 locus. BRG1-Tβ4 co-operative binding promotes optimal transcription of Wt1 as the master regulator of embryonic EPDCs. Moreover, chromatin immunoprecipitation-sequencing reveals BRG1 binding at further key loci suggesting SWI/SNF activity across the fetal epicardial gene programme. These findings reveal essential functions for chromatin-remodelling in the activation of EPDCs during cardiovascular development and repair.

Xin Sun

Papers

Macrophages directly contribute collagen to scar formation during zebrafish heart regeneration and mouse heart repair

Magnetic and structural studies of the Verwey transition in Fe3−δO4 nanoparticles

BRG1-SWI/SNF-dependent regulation of the Wt1 transcriptional landscape mediates epicardial activity during heart development and disease.