The synthesis of highly crystalline and monodisperse gamma-Fe(2)O(3) nanocrystallites is reported. High-temperature (300 degrees C) aging of iron-oleic acid metal complex, which was prepared by the thermal decomposition of iron pentacarbonyl in the presence of oleic acid at 100 degrees C, was found to generate monodisperse iron nanoparticles. The resulting iron nanoparticles were transformed to monodisperse gamma-Fe(2)O(3) nanocrystallites by controlled oxidation by using trimethylamine oxide as a mild oxidant. Particle size can be varied from 4 to 16 nm by controlling the experimental parameters. Transmission electron microscopic images of the particles showed 2-dimensional and 3-dimensional assembly of particles, demonstrating the uniformity of these nanoparticles. Electron diffraction, X-ray diffraction, and high-resolution transmission electron microscopic (TEM) images of the nanoparticles showed the highly crystalline nature of the gamma-Fe(2)O(3) structures. Monodisperse gamma-Fe(2)O(3) nanocrystallites with a particle size of 13 nm also can be generated from the direct oxidation of iron pentacarbonyl in the presence of oleic acid with trimethylamine oxide as an oxidant.

Various inorganic nanoparticles have been used as magnetic resonance imaging (MRI) contrast agents due to their unique properties, such as large surface area and efficient contrasting effect. Since the first use of superparamagnetic iron oxide (SPIO) as a liver contrast agent, nanoparticulate MRI contrast agents have attracted a lot of attention. Magnetic iron oxide nanoparticles have been extensively used as MRI contrast agents due to their ability to shorten T2* relaxation times in the liver, spleen, and bone marrow. More recently, uniform ferrite nanoparticles with high crystallinity have been successfully employed as new T2 MRI contrast agents with improved relaxation properties. Iron oxide nanoparticles functionalized with targeting agents have been used for targeted imaging via the site‐specific accumulation of nanoparticles at the targets of interest. Recently, extensive research has been conducted to develop nanoparticle‐based T1 contrast agents to overcome the drawbacks of iron oxide nanoparticle‐based negative T2 contrast agents. In this report, we summarize the recent progress in inorganic nanoparticle‐based MRI contrast agents.

Uniform and extremely small-sized iron oxide nanoparticles (ESIONs) of < 4 nm were synthesized via the thermal decomposition of iron-oleate complex in the presence of oleyl alcohol. Oleyl alcohol lowered the reaction temperature by reducing iron-oleate complex, resulting in the production of small-sized nanoparticles. XRD pattern of 3 nm-sized nanoparticles revealed maghemite crystal structure. These nanoparticles exhibited very low magnetization derived from the spin-canting effect. The hydrophobic nanoparticles can be easily transformed to water-dispersible and biocompatible nanoparticles by capping with the poly(ethylene glycol)-derivatized phosphine oxide (PO-PEG) ligands. Toxic response was not observed with Fe concentration up to 100 μg/mL in MTT cell proliferation assay of POPEG-capped 3 nm-sized iron oxide nanoparticles. The 3 nm-sized nanoparticles exhibited a high r(1) relaxivity of 4.78 mM(-1) s(-1) and low r(2)/r(1) ratio of 6.12, demonstrating that ESIONs can be efficient T(1) contrast agents. The high r(1) relaxivities of ESIONs can be attributed to the large number of surface Fe(3+) ions with 5 unpaired valence electrons. In the in vivo T(1)-weighted magnetic resonance imaging (MRI), ESIONs showed longer circulation time than the clinically used gadolinium complex-based contrast agent, enabling high-resolution imaging. High-resolution blood pool MR imaging using ESIONs enabled clear observation of various blood vessels with sizes down to 0.2 mm. These results demonstrate the potential of ESIONs as T(1) MRI contrast agents in clinical settings.

We report on the synthesis of semiconductor nanocrystals of PbS, ZnS, CdS, and MnS through a facile and inexpensive synthetic process. Metal-oleylamine complexes, which were obtained from the reaction of metal chloride and oleylamine, were mixed with sulfur. The reaction mixture was heated under appropriate experimental conditions to produce metal sulfide nanocrystals. Uniform cube-shaped PbS nanocrystals with particle sizes of 6, 8, 9, and 13 nm were synthesized. The particle size was controlled by changing the relative amount of PbCl(2) and sulfur. Uniform 11 nm sized spherical ZnS nanocrystals were synthesized from the reaction of zinc chloride and sulfur, followed by one cycle of size-selective precipitation. CdS nanocrystals that consist of rods, bipods, and tripods were synthesized from a reaction mixture containing a 1:6 molar ratio of cadmium to sulfur. Spherical CdS nanocrystals (5.1 nm sized) were obtained from a reaction mixture with a cadmium to sulfur molar ratio of 2:1. MnS nanocrystals with various sizes and shapes were synthesized from the reaction of MnCl(2) and sulfur in oleylamine. Rod-shaped MnS nanocrystals with an average size of 20 nm (thickness) x 37 nm (length) were synthesized from a 1:1 molar ratio of MnCl(2) and sulfur at 240 degrees C. Novel bullet-shaped MnS nanocrystals with an average size of 17 nm (thickness) x 44 nm (length) were synthesized from the reaction of 4 mmol of MnCl(2) and 2 mmol of sulfur at 280 degrees C for 2 h. Shorter bullet-shaped MnS nanocrystals were synthesized from a 3:1 molar ratio of MnCl(2) and sulfur. Hexagon-shaped MnS nanocrystals were also obtained. All of the synthesized nanocrystals were highly crystalline.

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Contrasting images: A new T1 contrast agent for magnetic resonance imaging (MRI) based on MnO nanoparticles reveals a bright signal enhancement and fine anatomic structures in the T1‐weighted MR image of a mouse brain (see picture; left MRI, right MnO‐enhanced MRI (MONEMRI)). Furthermore, MnO nanoparticles conjugated with a tumor‐specific antibody were used for selectively imaging breast cancer cells in a metastatic tumor in brain.

We synthesized Ni/Pd core/shell nanoparticles from the consecutive thermal decomposition of metal-surfactant complexes. The nanoparticle catalyst was atom-economically applied for various Sonogashira coupling reactions.

Core/shell upconverting nanoparticles (UCNPs) of NaGdF4:Er3+,Yb3+/NaGdF4 (see figure) are shown to serve as a multimodal imaging probe that works for both background‐free optical imaging and magnetic resonance imaging (MRI). The nonblinking and nonbleaching properties of UCNPs can contribute to minimization of possible artifacts in long‐term imaging experiments. Owing to Gd3+ ions in the host matrix, contrast is enhanced in T1‐weighted MRI.