The interest in nanoscale materials stems from the fact that new properties are acquired at this length scale and, equally important, that these properties * To whom correspondence should be addressed. Phone, 404-8940292; fax, 404-894-0294; e-mail, mostafa.el-sayed@ chemistry.gatech.edu. † Case Western Reserve UniversitysMillis 2258. ‡ Phone, 216-368-5918; fax, 216-368-3006; e-mail, burda@case.edu. § Georgia Institute of Technology. 1025 Chem. Rev. 2005, 105, 1025−1102

Chemistry and properties of nanocrystals of different shapes.

Synthesis and surface engineering of iron oxide nanoparticles for biomedical applications

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

Nanocrystals are fundamental to modern science and technology. Mastery over the shape of a nanocrystal enables control of its properties and enhancement of its usefulness for a given application. Our aim is to present a comprehensive review of current research activities that center on the shape-controlled synthesis of metal nanocrystals. We begin with a brief introduction to nucleation and growth within the context of metal nanocrystal synthesis, followed by a discussion of the possible shapes that a metal nanocrystal might take under different conditions. We then focus on a variety of experimental parameters that have been explored to manipulate the nucleation and growth of metal nanocrystals in solution-phase syntheses in an effort to generate specific shapes. We then elaborate on these approaches by selecting examples in which there is already reasonable understanding for the observed shape control or at least the protocols have proven to be reproducible and controllable. Finally, we highlight a number of applications that have been enabled and/or enhanced by the shape-controlled synthesis of metal nanocrystals. We conclude this article with personal perspectives on the directions toward which future research in this field might take.

Shape‐Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?

5.1. Nanoalloys of Group 11 (Cu, Ag, Au) 865 5.1.1. Cu−Ag 866 5.1.2. Cu−Au 867 5.1.3. Ag−Au 870 5.1.4. Cu−Ag−Au 872 5.2. Nanoalloys of Group 10 (Ni, Pd, Pt) 872 5.2.1. Ni−Pd 872 * To whom correspondence should be addressed. Phone: +39010 3536214. Fax:+39010 311066. E-mail: ferrando@fisica.unige.it. † Universita di Genova. ‡ Argonne National Laboratory. § University of Birmingham. | As of October 1, 2007, Chemical Sciences and Engineering Division. Volume 108, Number 3

Nanoalloys: From Theory to Applications of Alloy Clusters and Nanoparticles

A method is reported for the fabrication of wires with extended pore structures. Nanospheres are initially infiltrated into the one-dimensional channels of alumina or polymer porous membranes. Metal is then electrochemically deposited within the channels. Removal of the membrane and nanospheres results in porous wires. The production of 1-μm diameter wires with 300- or 500-nm diameter pores and 300-nm diameter wires with 140-nm pores illustrates the utility of this approach. Contacts between the spheres and the channel wall result in openings on the surface of the wires, and contacts between the spheres themselves produce openings between adjacent pores. Some short-range ordering of the spheres within the channels, as reflected in the wire pore structure, is evident. Characterization of the porous wires by electron microscopy is presented, and the potential applications of materials is discussed.

Synthesis of porous wires from directed assemblies of nanospheres.

Pure metal iron nanoparticles are unstable in the air. By a coating iron on nanoparticle surface with a stable noble metal, these air-stable nanoparticles are protected from the oxidation and retain most of the favorable magnetic properties, which possess the potential application in high density memory device by forming self-assembling nanoarrays. Gold-coated iron core-shell structure nanoparticles (Fe/Au) synthesized using reverse micelles were characterized by transmission electron microscopy (TEM). The average nanoparticle size of the core-shell structure is about 8 nm, with about 6 nm diameter core and 1∼2 nm shell. Since the gold shell is not epitaxial growth related to the iron core, the morie pattern can be seen from the overlapping of iron core and gold shell. However, the gold shell lattice can be seen by changing the defocus of TEM. An energy dispersive X-ray spectrum (EDS) also shows the nanoparticles are air-stable. The magnetic measurement of the nanoparticles also proved successful synthesis of gold coated iron core-shell structure. The nanoparticles were then assembled under 0.5 T magnetic field and formed parallel nanobands with about 10 μm long. Assembling two dimensional ordered nanoarrays are still under going.

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Nanostructures of gold coated iron core-shell nanoparticles and the nanobands assembled under magnetic field

A low-temperature topotactic route is used to assemble metal−anion arrays within a perovskite host. Ion exchange between RbLaNb2O7 and CuX2 (X = Cl, Br) results in a new set of layered copper−oxyhalide perovskites, (CuX)LaNb2O7. Rietveld structural analysis of X-ray powder diffraction data confirms the formation of a two-dimensional copper−halide network in the double-layered perovskite interlayer. This new structure type contains unusual CuO2X4 octahedra that corner-share with NbO6 octahedra from the perovskite slab and edge-share with each other along all four equatorial edges. Magnetic susceptibility measurements show that both products exhibit antiferromagnetic transitions below 40 K. Additionally, these materials are found to be low-temperature phases, decomposing completely by 700 °C. The synthetic approach described in this work is significant in that it demonstrates how host structures can be used as templates in the directed low-temperature assembly of extended metal−anion arrays.

Assembly of Metal−Anion Arrays within a Perovskite Host. Low-Temperature Synthesis of New Layered Copper−Oxyhalides, (CuX)LaNb2O7, X = Cl, Br

In this article, metallic iron, and iron/platinum alloys nanoparticles have been synthesized via chemical assembly and magnetically characterized. Fabrication of iron and iron/platinum particles was achieved by reducing 0.1 M aqueous metal salts confined in the polar portions of inverse micelles of cetyltrimethylammonium bromide with borohydride. The dc susceptibility of a sample of 8 nm iron nanoparticles exhibits a blocking temperature of 54 K and coercivity of 200 G at 10 K. The presence of the gold coatings prevented oxidation and allowed the samples to be manipulated without additional precautions to prevent oxidation. Two iron/platinum alloys have been synthesized and verified by x-ray powder diffraction and transmission electron microscopy. Magnetic characterization is performed using superconducting quantum interference device magnetometry.

Weilie L. Zhou

Papers

Synthesis of porous wires from directed assemblies of nanospheres.

Nanostructures of gold coated iron core-shell nanoparticles and the nanobands assembled under magnetic field

Assembly of Metal−Anion Arrays within a Perovskite Host. Low-Temperature Synthesis of New Layered Copper−Oxyhalides, (CuX)LaNb2O7, X = Cl, Br

Magnetic properties of iron and iron platinum alloys synthesized via microemulsion techniques

Electrodeposited nickel and gold nanoscale metal meshes with potentially interesting photonic properties