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Self-assembled monolayers of thiolates on metals as a form of nanotechnology.

This review focuses on the synthesis, protection, functionalization, and application of magnetic nanoparticles, as well as the magnetic properties of nanostructured systems. Substantial progress in the size and shape control of magnetic nanoparticles has been made by developing methods such as co-precipitation, thermal decomposition and/or reduction, micelle synthesis, and hydrothermal synthesis. A major challenge still is protection against corrosion, and therefore suitable protection strategies will be emphasized, for example, surfactant/polymer coating, silica coating and carbon coating of magnetic nanoparticles or embedding them in a matrix/support. Properly protected magnetic nanoparticles can be used as building blocks for the fabrication of various functional systems, and their application in catalysis and biotechnology will be briefly reviewed. Finally, some future trends and perspectives in these research areas will be outlined.

Magnetic nanoparticles: Synthesis, protection, functionalization, and application

1. Introduction 20642. Synthesis of Magnetic Nanoparticles 20662.1. Classical Synthesis by Coprecipitation 20662.2. Reactions in Constrained Environments 20682.3. Hydrothermal and High-TemperatureReactions20692.4. Sol-Gel Reactions 20702.5. Polyol Methods 20712.6. Flow Injection Syntheses 20712.7. Electrochemical Methods 20712.8. Aerosol/Vapor Methods 20712.9. Sonolysis 20723. Stabilization of Magnetic Particles 20723.1. Monomeric Stabilizers 20723.1.1. Carboxylates 20733.1.2. Phosphates 20733.2. Inorganic Materials 20733.2.1. Silica 20733.2.2. Gold 20743.3. Polymer Stabilizers 20743.3.1. Dextran 20743.3.2. Polyethylene Glycol (PEG) 20753.3.3. Polyvinyl Alcohol (PVA) 20753.3.4. Alginate 20753.3.5. Chitosan 20753.3.6. Other Polymers 20753.4. Other Strategies for Stabilization 20764. Methods of Vectorization of the Particles 20765. Structural and Physicochemical Characterization 20785.1. Size, Polydispersity, Shape, and SurfaceCharacterization20795.2. Structure of Ferro- or FerrimagneticNanoparticles20805.2.1. Ferro- and Ferrimagnetic Nanoparticles 20805.3. Use of Nanoparticles as Contrast Agents forMRI20825.3.1. High Anisotropy Model 20845.3.2. Small Crystal and Low Anisotropy EnergyLimit20855.3.3. Practical Interests of Magnetic NuclearRelaxation for the Characterization ofSuperparamagnetic Colloid20855.3.4. Relaxation of Agglomerated Systems 20856. Applications 20866.1. MRI: Cellular Labeling, Molecular Imaging(Inﬂammation, Apoptose, etc.)20866.2.

Magnetic Iron Oxide Nanoparticles: Synthesis, Stabilization, Vectorization, Physicochemical Characterizations, and Biological Applications

The development of nanocrystals has been intensively pursued, not only for their fundamental scientific interest, but also for many technological applications. The synthesis of monodisperse nanocrystals (size variation <5%) is of key importance, because the properties of these nanocrystals depend strongly on their dimensions. For example, the colour sharpness of semiconductor nanocrystal-based optical devices is strongly dependent on the uniformity of the nanocrystals, and monodisperse magnetic nanocrystals are critical for the next-generation multi-terabit magnetic storage media. For these monodisperse nanocrystals to be used, an economical mass-production method needs to be developed. Unfortunately, however, in most syntheses reported so far, only sub-gram quantities of monodisperse nanocrystals were produced. Uniform-sized nanocrystals of CdSe (refs 10,11) and Au (refs 12,13) have been produced using colloidal chemical synthetic procedures. In addition, monodisperse magnetic nanocrystals such as Fe (refs 14,15), Co (refs 16-18), gamma-Fe(2)O(3) (refs 19,20), and Fe(3)O(4) (refs 21,22) have been synthesized by using various synthetic methods. Here, we report on the ultra-large-scale synthesis of monodisperse nanocrystals using inexpensive and non-toxic metal salts as reactants. We were able to synthesize as much as 40 g of monodisperse nanocrystals in a single reaction, without a size-sorting process. Moreover, the particle size could be controlled simply by varying the experimental conditions. The current synthetic procedure is very general and nanocrystals of many transition metal oxides were successfully synthesized using a very similar procedure.

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Ultra-large-scale syntheses of monodisperse nanocrystals.

High-temperature solution phase reaction of iron(III) acetylacetonate, Fe(acac)3, with 1,2-hexadecanediol in the presence of oleic acid and oleylamine leads to monodisperse magnetite (Fe3O4) nanoparticles. Similarly, reaction of Fe(acac)3 and Co(acac)2 or Mn(acac)2 with the same diol results in monodisperse CoFe2O4 or MnFe2O4 nanoparticles. Particle diameter can be tuned from 3 to 20 nm by varying reaction conditions or by seed-mediated growth. The as-synthesized iron oxide nanoparticles have a cubic spinel structure as characterized by HRTEM, SAED, and XRD. Further, Fe3O4 can be oxidized to Fe2O3, as evidenced by XRD, NEXAFS spectroscopy, and SQUID magnetometry. The hydrophobic nanoparticles can be transformed into hydrophilic ones by adding bipolar surfactants, and aqueous nanoparticle dispersion is readily made. These iron oxide nanoparticles and their dispersions in various media have great potential in magnetic nanodevice and biomagnetic applications.

Monodisperse MFe2O4 (M = Fe, Co, Mn) Nanoparticles

The synthesis of highly crystalline and monodisperse γ-Fe2O3 nanocrystallites is reported. High-temperature (300 °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 °C, was found to generate monodisperse iron nanoparticles. The resulting iron nanoparticles were transformed to monodisperse γ-Fe2O3 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 γ-Fe2O3 structures. Monodisperse γ-Fe2O3 nanocrystallites with a particle size of 13 nm also can be...

http://www.geocities.ws/nandwana_vikas/Synthesis_of_Highly_Crystalline_and_Monodisperse_Maghemite.pdf

Synthesis of highly crystalline and monodisperse maghemite nanocrystallites without a size-selection process.

Quantum dots (QDs) and magnetic nanoparticles (MPs) are of interest for biological imaging, drug targeting, and bioconjugation because of their unique optoelectronic and magnetic properties, respectively. To provide for water solubility and biocompatibility, QDs and MPs were encapsulated within a silica shell using a reverse microemulsion synthesis. The resulting SiO2/MP-QD nanocomposite particles present a unique combination of magnetic and optical properties. Their nonporous silica shell allows them to be surface modified for bioconjugation in various biomedical applications.

Silica-coated nanocomposites of magnetic nanoparticles and quantum dots.

Reverse microemulsion techniques combined with templating strategies have led to the synthesis of four types of nanoparticles. First, homogeneous SiO2-coated Fe2O3 (SiO2/Fe2O3) nanoparticles with controlled SiO2 shell thickness (1.8−30 nm) were synthesized by reverse microemulsion. These nanocomposite particles were used as templates for the deposition of a mesoporous silica shell. The iron oxide core in SiO2/Fe2O3 could be partially and completely etched to produce rattle-type SiO2/Fe2O3 nanoballs and hollow SiO2 nanoballs, respectively. These facile synthetic methods led to the formation of different nanoparticle architectures with tailored silica shell thickness and porosity.

Nanoparticle Architectures Templated by SiO2/Fe2O3 Nanocomposites

Engineered nanomedicines with enhanced tumor penetration

Highly crystalline and monodisperse cobalt ferrite nanocrystals were fabricated by the high-temperature aging of a metal−surfactant complex followed by mild oxidation. Particle sizes were varied from 4 to 9 nm by changing the experimental conditions. Transmission electron microscopic (TEM) images of the particles showed two- and three-dimensional assembly of the particles, demonstrating the uniformity of the nanocrystals. Electron diffraction, X-ray diffraction, and high-resolution transmission electron microscopic images of the nanocrystals confirmed the highly crystalline nature of the cobalt ferrite structure. The elemental analysis confirmed the stoichiometry of cobalt ferrite, despite some variations in the relative atomic composition of nanocrystals. The nanocrystals were found to have typical behaviors of magnetic nanocrystals and the narrow energy barrier distributions of magnetic anisotropy, implying that the nanocrystals obtained are very uniform.

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Su Seong Lee

Papers

Synthesis of highly crystalline and monodisperse maghemite nanocrystallites without a size-selection process.

Silica-coated nanocomposites of magnetic nanoparticles and quantum dots.

Nanoparticle Architectures Templated by SiO2/Fe2O3 Nanocomposites

Engineered nanomedicines with enhanced tumor penetration

Synthesis of Highly Crystalline and Monodisperse Cobalt Ferrite Nanocrystals