Surface functionalization of self-organized TiO 2 nanotube (NT) arrays produced by electrochemical anodization is implemented by dextrin-coated iron-oxide nanoparticles leading to a composite semiconductor nanostructure. The morphological and structural properties are studied by electron and atomic force microscopy, X-ray diffraction, X-ray photoelectron, and resonance micro-Raman spectroscopies revealing successful deposition of maghemite (γ-Fe 2 O 3 ) nanoparticles on the nanotube walls. The nanocomposite surface simultaneously exhibits high photocatalytic activity for the degradation of model pollutants under UV irradiation at relatively low loading levels of the γ-Fe 2 O 3 nanoparticles and light-independent wetting properties, as the initially superhydrophilic surface is converted to a moderately hydrophilic substrate, while obtaining an additional functionality through the magnetic field response of the iron-oxide component that shows appreciable magnetization anisotropy. Electrochemical impedance investigation including Mott-Schottky analysis attests to a significant improvement of the interfacial electron-transfer kinetics together with a modification of the surface chemistry for the functionalized TiO 2 nanotubes, promoting electron-hole separation through the polyhydroxyl dextrin shell that mediates charge transfer between the constituent semiconductor oxides and validating their improved photocatalytic performance. These composite nanotubular materials offer the opportunity of advanced applications, where the unique photoinduced reactivity, the controlled wetting behavior, and the magnetic field response can be effectively combined.
One of the most significant challenges implementing colloidal magnetic nanoparticles in medicine is the efficient heating of microliter quantities by applying a low frequency alternating magnetic field. The ultimate goal is to accomplish nonsurgically the treatment of millimeter size tumors. Here, we demonstrate the synthesis, characterization, and the in vitro as well as in vivo efficiency of a dextran coated maghemite (gamma-Fe(2)O(3)) ferrofluid with an exceptional response to magnetic heating. The difference to previous synthetic attempts is the high charge of the dextran coating, which according to our study maintains the colloidal stability and good dispersion of the ferrofluid during the magnetic heating stage. Specifically, in vitro 2 mul of the ferrofluid gives an outstanding temperature rise of 33 degrees C within 10 min, while in vivo treatment, by infusing 150 mul of the ferrofluid in animal model (rat) glioma tumors, causes an impressive cancer tissue dissolution.
The structural and magnetic properties and spin dynamics of dextran coated and uncoated γ-Fe(2)O(3) (maghemite) nanoparticles have been investigated using high resolution transmission electron microscopy (HRTEM), (57)Fe nuclear magnetic resonance (NMR), Mössbauer spectroscopy and dc magnetization measurements. The HRTEM observations indicated a well-crystallized system of ellipsoid-shaped nanoparticles, with an average size of 10 nm. The combined Mössbauer and magnetic study suggested the existence of significant interparticle interactions not only in the uncoated but also in the dextran coated nanoparticle assemblies. The zero-field NMR spectra of the nanoparticles at low temperatures are very similar to those of the bulk material, indicating the same hyperfine field values at saturation in accord with the performed Mössbauer measurements. The T(2) NMR spin-spin relaxation time of the nanoparticles has also been measured as a function of temperature and found to be two orders of magnitude shorter than that of the bulk material. It is shown that the thermal fluctuations in the longitudinal magnetization of the nanoparticles in the low temperature limit may account for the shortening and the temperature dependence of the T(2) relaxation time. Thus, the low temperature NMR results are in accord with the mechanism of collective magnetic excitations, due to the precession of the magnetization around the easy direction of the magnetization at an energy minimum, a mechanism originally proposed to interpret Mössbauer experiments in magnetic nanoparticles. The effect of the surface spins on the NMR relaxation mechanisms is also discussed.
The influence of coating on interparticle interactions in ferrofluids has been investigated using various techniques such as Mossbauer spectroscopy, magnetometry, transmission electron microscopy, photon correlation spectroscopy, X-ray diffraction, X-ray photoelectron, and resonance micro-Raman spectroscopy. Aging and spin-glass-like behavior was investigated in frozen ferrofluids of various concentrations from dense, initial value of 40 mg of coated nanoparticles per 1 mL of water, to dilute 1:10 (4 mg/mL). The as-prepared nanoparticles, core size 7-8 nm, were subsequently coated with a gummic acid corona of 20 nm thickness, which was observed to prevent agglomeration and to delay aggregation even in dense ferrofluids. The resulting separation of magnetic cores due to the coating eliminated all magnetic interparticle interaction mechanisms, such as exchange and dipoledipole, thus ensuring no aging effects of the magnetic particle system, as manifested in particle agglomeration and precipitation.
Ultrasmall superparamagnetic iron oxide nanoparticles coated with gummic acid have been investigated as possible constituents of aqueous ferrofluids for biomedical applications and especially for MRI contrast agent. The structural characteristics and the size of the nanoparticles have been analyzed as well as the magnetic properties. In order to evaluate any possible capabilities as a contrast agent, the relaxation time, T2, of hydrogen protons in the colloidal solutions of nanoparticles have been measured in order to gain information on the relaxation behavior compared to other MRI contrast agents. The in vitro cytotoxicity of the obtained magnetic nanoparticles of iron oxide coated with gummic acid was investigated by two separate methods ͑MTT and FACS analysis͒ and by using three different normal and transformed cell lines. Our results showed that the synthesized nanoparticles had no toxic effect on any of the cell lines used.
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