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.

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

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.

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

Nanoparticle- and quantum-dot (QD)-based bioprobes are emerging as alternatives to small-molecule probes for in vitro and in vivo applications However, their cellular interaction and cell uptake mechanism are significantly different from those of small-molecule probes and are extremely sensitive to surface ligands These present a barrier in the development of nanoparticles and QDs as cellular probes This work focused on the synthesis of various functionalized QDs with tunable surface charge, hydrophobicity, and functionalization with poly(ethylene glycol) (PEGylation) and their cellular interaction We found that the surface functional groups of nanometer-sized probes significantly dictated their cellular interaction, subcellular localization, and cytotoxicity A dose-dependent interaction was observed for all types of QDs, but the cationic surface charge or hydrophobicity would increase the cellular interaction as compared to the anionic surface charge Cationic QDs rapidly entered cells and induced c

Surface-Ligand-Dependent Cellular Interaction, Subcellular Localization, and Cytotoxicity of Polymer-Coated Quantum Dots

Proceedings of the Chemical Society. November 1962

Inhibition of amyloid fibrillation and clearance of amyloid fibrils/plaques are essential for the prevention and treatment of various neurodegenerative disorders involving protein aggregation. Herein, we report curcumin-functionalized gold nanoparticles (Au-curcumin) of hydrodynamic diameter 10-25 nm, which serve to inhibit amyloid fibrillation and disintegrate/dissolve amyloid fibrils. In nanoparticle form, curcumin is water-soluble and can efficiently interact with amyloid protein/peptide, offering enhanced performance in inhibiting amyloid fibrillation and dissolving amyloid fibrils. Our results imply that nanoparticle-based artificial molecular chaperones may offer a promising therapeutic approach to combat neurodegenerative disease.

Inhibition of Amyloid Fibril Growth and Dissolution of Amyloid Fibrils by Curcumin–Gold Nanoparticles

A graphene based composite with copper nanoparticles (Cu–G) has been synthesized and used as catalyst for N-arylation and O-arylation. The structure and composition of the nanocomposite have been characterized by TEM, AFM, Raman and XPS. The catalytic activity of the Cu–G has been tested for the N-arylation of N–H heterocycles using arylboronic acids and the O-arylation of phenols using aryl halides. The catalytic N-arylation produces N-aryl heterocyles and the catalytic O-arylation produces diaryl ethers, under mild reaction conditions with excellent yields and selectivities. The developed catalyst is air-stable, inexpensive, easy to prepare, easy to recover by simple filtration and can be reused without appreciable loss of activity.

Enhanced catalytic performance by copper nanoparticle–graphene based composite

Glutathione (GSH) and oxidized glutathione (GSSG) control cellular function and efficiency of anticancer therapy. Reliable detection of cellular GSH/GSSG is challenging due to their ultralow concentration (typically femtomolar concentrations) and interference by other thiol-based molecules. Here, we report a “turn-off” surface enhanced Raman scattering (SERS)-based approach for reliable detection of cellular GSH and GSSG. This approach exploits GSH-induced replacement of a Raman probe from the surface of γ-Fe2O3–Au followed by Ag growth around γ-Fe2O3–Au that generates electromagnetic hot spots at the junction between Au and Ag where the Raman probe is localized. The magnetic component of the hybrid nanoparticle concentrates the cellular GSH, and the Au/Ag-based plasmonic component provides electromagnetic hot spots for sensitive SERS. This approach is able to monitor GSH level during photothermal cancer therapy.

Nikhil R. Jana

Papers

Surface-Ligand-Dependent Cellular Interaction, Subcellular Localization, and Cytotoxicity of Polymer-Coated Quantum Dots

Proceedings of the Chemical Society. November 1962

Inhibition of Amyloid Fibril Growth and Dissolution of Amyloid Fibrils by Curcumin–Gold Nanoparticles

Enhanced catalytic performance by copper nanoparticle–graphene based composite

Detection of cellular glutathione and oxidized glutathione using magnetic-plasmonic nanocomposite-based "turn-off" surface enhanced Raman scattering.