Although gold is the subject of one of the most ancient themes of investigation in science, its renaissance now leads to an exponentially increasing number of publications, especially in the context of emerging nanoscience and nanotechnology with nanoparticles and self-assembled monolayers (SAMs). We will limit the present review to gold nanoparticles (AuNPs), also called gold colloids. AuNPs are the most stable metal nanoparticles, and they present fascinating aspects such as their assembly of multiple types involving materials science, the behavior of the individual particles, size-related electronic, magnetic and optical properties (quantum size effect), and their applications to catalysis and biology. Their promises are in these fields as well as in the bottom-up approach of nanotechnology, and they will be key materials and building block in the 21st century. Whereas the extraction of gold started in the 5th millennium B.C. near Varna (Bulgaria) and reached 10 tons per year in Egypt around 1200-1300 B.C. when the marvelous statue of Touthankamon was constructed, it is probable that “soluble” gold appeared around the 5th or 4th century B.C. in Egypt and China. In antiquity, materials were used in an ecological sense for both aesthetic and curative purposes. Colloidal gold was used to make ruby glass 293 Chem. Rev. 2004, 104, 293−346

Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

The surface science of titanium dioxide

Self-assembly is the autonomous organization of components into patterns or structures without human intervention. Self-assembling processes are common throughout nature and technology. They involve components from the molecular (crystals) to the planetary (weather systems) scale and many different kinds of interactions. The concept of self-assembly is used increasingly in many disciplines, with a different flavor and emphasis in each.

http://science.sciencemag.org/content/sci/295/5564/2418.full.pdf

Self-assembly at all scales.

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

This article presents an overview of current research activities that center on monodispersed colloidal spheres whose diameter falls anywhere in the range of 10 nm to 1 μm. It is organized into three parts: The first part briefly discusses several useful methods that have been developed for producing monodispersed colloidal spheres with tightly controlled sizes and well-defined properties (both surface and bulk). The second part surveys some techniques that have been demonstrated for organizing these colloidal spheres into two- and three-dimensionally ordered lattices. The third part highlights a number of unique applications of these crystalline assemblies, such as their uses as photonic bandgap (PBG) crystals; as removable templates to fabricate macroporous materials with highly ordered and three-dimensionally interconnected porous structures; as physical masks in lithographic patterning; and as diffractive elements to fabricate new types of optical sensors. Finally, we conclude with some personal perspectives on the directions towards which future research in this area might be directed.

Monodispersed Colloidal Spheres: Old Materials with New Applications

This paper describes a sol−gel approach for the coating of superparamagnetic iron oxide nanoparticles with uniform shells of amorphous silica. The coating process has been successfully applied to particles contained in a commercial ferrofluid (e.g., the EMG 304 of Ferrofluidics) and those synthesized through a wet chemical process. The thickness of silica coating could be conveniently controlled in the range of 2−100 nm by changing the concentration of the sol−gel solution. Fluorescent dyes, for example, 7-(dimethylamino)-4-methylcoumarin-3-isothiocyanate (DACITC) and tetramethylrhodamine-5-isothiocyanate (5-TRITC), have also been incorporated into the silica shells by covalently coupling these organic compounds with the sol−gel precursor. These multifunctional nanoparticles are potentially useful in a number of areas because they can be simultaneously manipulated with an externally applied magnetic field and characterized in situ using conventional fluorescence microscopy.

Modifying the Surface Properties of Superparamagnetic Iron Oxide Nanoparticles through A Sol−Gel Approach

This paper describes a strategy that combines physical templating and capillary forces to assemble monodispersed spherical colloids into uniform aggregates with well-controlled sizes, shapes, and structures. When an aqueous dispersion of colloidal particles was allowed to dewet from a solid surface that had been patterned with appropriate relief structures, the particles were trapped by the recessed regions and assembled into aggregates whose structures were determined by the geometric confinement provided by the templates. We have demonstrated the capability and feasibility of this approach by assembling polystyrene beads and silica colloids (> or =150 nm in diameter) into complex aggregates that include polygonal or polyhedral clusters, linear or zigzag chains, and circular rings. We have also been able to generate hybrid aggregates in the shape of HF or H2O molecules that are composed of polymer beads having different diameters, polymer beads labeled with different organic dyes, and a combination of polymeric and inorganic beads. These colloidal aggregates can serve as a useful model system to investigate the hydrodynamic and optical scattering properties of colloidal particles having nonspherical morphologies. They should also find use as the building blocks to generate hierarchically self-assembled systems that may exhibit interesting properties highly valuable to areas ranging from photonics to condensed matter physics.

Template-assisted self-assembly: a practical route to complex aggregates of monodispersed colloids with well-defined sizes, shapes, and structures.

Gold nanoparticles have been conformally coated with amorphous silica (using a sol−gel method) and then an organic polymer (via surface-grafted, atom transfer radical polymerization) to form spherical colloids with a core−double-shell structure. The thickness of silica and polymer shells could be conveniently controlled in the range of tens to several hundred nanometers by changing the concentration of the reagent and/or the reaction time. Selective removal of the silica layer (through etching in aqueous HF) led to the formation of hollow polymer beads containing movable gold cores. This new form of core−shell particles provides a unique system for measuring the feature size and transport property associated with hollow particles. In one demonstration, we showed that the thickness of a closed polymer shell could be obtained by mapping the electrons backscattered from the core and shell. In another demonstration, the plasmon resonance band of the gold cores was used as an optical probe to follow the diffus...

Synthesis and characterization of monodispersed core-shell spherical colloids with movable cores.

Gold nanoparticles have been coated with amorphous silica to form spherical colloids with a core−shell structure The thickness of silica shells could be conveniently controlled in the range of tens to several hundred nanometers by changing the concentration of the sol−gel precursor or the coating time These core−shell colloids could serve as the building blocks to fabricate photonic devices In one demonstration, we showed that these core−shell particles could be assembled into long-range ordered lattices (or photonic crystals) over large areas that exhibited optical properties different from those crystallized from silica colloids Transmission spectra of these crystals displayed both features that correspond to the Bragg diffraction of a periodic lattice and the plasmon resonance absorption of gold nanoparticles Reflectance spectra taken from these crystals only showed peaks caused by Bragg diffraction In another demonstration, these core−shell colloids were assembled into chains of different config

Yu Lu

Papers

Monodispersed Colloidal Spheres: Old Materials with New Applications

Modifying the Surface Properties of Superparamagnetic Iron Oxide Nanoparticles through A Sol−Gel Approach

Template-assisted self-assembly: a practical route to complex aggregates of monodispersed colloids with well-defined sizes, shapes, and structures.

Synthesis and characterization of monodispersed core-shell spherical colloids with movable cores.

Synthesis and Self-Assembly of Au@SiO2 Core−Shell Colloids