We report a general thermal transformation approach to synthesize single-crystalline magnetic transition metal oxides nanotubes/nanorings including magnetite Fe(3)O(4), maghematite gamma-Fe(2)O(3), and ferrites MFe(2)O(4) (M = Co, Mn, Ni, Cu) using hematite alpha-Fe(2)O(3) nanotubes/nanorings template. While the straightforward reduction or reduction-oxides process was employed to produce Fe(3)O(4) and gamma-Fe(2)O(3), the alpha-Fe(2)O(3)/M(OH)(2) core/shell nanostructure was used as precursor to prepare MFe(2)O(4) nanotubes via MFe(2)O(4-x) (0 < x < 1) intermediate. The transformed ferrites nanocrystals retain the hollow structure and single-crystalline nature of the original templates. However, the crystallographic orientation-relationships of cubic spinel ferrites and trigonal hematite show strong correlation with their morpologies. The hollow-structured MFe(2)O(4) nanocrystals with tunable size, shape, and composition have exhibited unique magnetic properties. Moreover, they have been demonstrated as a highly effective peroxidase mimic catalysts for laboratory immunoassays or as a universal nanocapsules hybridized with luminescent QDs for magnetic separation and optical probe of lung cancer cells, suggesting that these biocompatible magnetic nanotubes/nanorings have great potential in biomedicine and biomagnetic applications.
In the present study, quantum dot (QD) capped magnetite nanorings (NRs) with a high luminescence and magnetic vortex core have been successfully developed as a new class of magnetic-fluorescent nanoprobe. Through electrostatic interaction, cationic polyethylenimine (PEI) capped QD have been firmly graft into negatively charged magnetite NRs modified with citric acid on the surface. The obtained biocompatible multicolor QD capped magnetite NRs exhibit a much stronger magnetic resonance (MR) T2* effect where the r2* relaxivity and r2*/r1 ratio are 4 times and 110 times respectively larger than those of a commercial superparamagnetic iron oxide. The multiphoton fluorescence imaging and cell uptake of QD capped magnetite NRs are also demonstrated using MGH bladder cancer cells. In particular, these QD capped magnetite NRs can escape from endosomes and be released into the cytoplasm. The obtained results from these exploratory experiments suggest that the cell-penetrating QD capped magnetite NRs could be an excellent dual-modality nanoprobe for intracellular imaging and therapeutic applications. This work has shown great potential of the magnetic vortex core based multifunctional nanoparticle as a high performance nanoprobe for biomedical applications.
The present study reports room-temperature ferromagnetic behaviors in three-dimensional (3D)-aligned thiol-capped single-crystalline ZnO nanowire (NW) and nanotube (NT) arrays as well as polycrystalline ZnO NT arrays. Besides the observation of height-dependent saturation magnetization, a much higher M(s) of 166 microemu cm(-2) has been found in NTs compared to NWs (36 microemu cm(-2)) due to larger surface area in ZnO NTs, indicating morphology-dependent magnetic properties in ZnO NW/NT systems. Density functional calculations have revealed that the origin of ferromagnetism is mainly attributed to spin-polarized 3p electrons in S sites and, therefore, has a strong correlation with Zn-S bond anisotropy. The preferential magnetization direction of both single-crystalline NTs and NWs lies perpendicular to the tube/wire axis due to the aligned high anisotropy orientation of the Zn-S bonds on the lateral (100) face of ZnO NWs and NTs. Polycrystalline ZnO NTs, however, exhibit a preferential magnetization direction parallel to the tube axis which is ascribed to shape anisotropy dominating the magnetic response. Our results demonstrate the interplay of morphology, dimensions, and crystallinity on spin alignment and magnetic anisotropy in a 3D semiconductor nanosystem with interfacial magnetism.
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