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.

Fundamentals of Plasmonics.- Electromagnetics of Metals.- Surface Plasmon Polaritons at Metal / Insulator Interfaces.- Excitation of Surface Plasmon Polaritons at Planar Interfaces.- Imaging Surface Plasmon Polariton Propagation.- Localized Surface Plasmons.- Electromagnetic Surface Modes at Low Frequencies.- Applications.- Plasmon Waveguides.- Transmission of Radiation Through Apertures and Films.- Enhancement of Emissive Processes and Nonlinearities.- Spectroscopy and Sensing.- Metamaterials and Imaging with Surface Plasmon Polaritons.- Concluding Remarks.

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Plasmonics: Fundamentals and Applications

The selection of nanoparticles for achieving efficient contrast for biological and cell imaging applications, as well as for photothermal therapeutic applications, is based on the optical properties of the nanoparticles. We use Mie theory and discrete dipole approximation method to calculate absorption and scattering efficiencies and optical resonance wavelengths for three commonly used classes of nanoparticles:  gold nanospheres, silica−gold nanoshells, and gold nanorods. The calculated spectra clearly reflect the well-known dependence of nanoparticle optical properties viz. the resonance wavelength, the extinction cross-section, and the ratio of scattering to absorption, on the nanoparticle dimensions. A systematic quantitative study of the various trends is presented. By increasing the size of gold nanospheres from 20 to 80 nm, the magnitude of extinction as well as the relative contribution of scattering to the extinction rapidly increases. Gold nanospheres in the size range commonly employed (∼40 nm)...

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Calculated Absorption and Scattering Properties of Gold Nanoparticles of Different Size, Shape, and Composition: Applications in Biological Imaging and Biomedicine

We present a simple and intuitive picture, an electromagnetic analog of molecular orbital theory, that describes the plasmon response of complex nanostructures of arbitrary shape. Our model can be understood as the interaction or "hybridization" of elementary plasmons supported by nanostructures of elementary geometries. As an example, the approach is applied to the important case of a four-layer concentric nanoshell, where the hybridization of the plasmons of the inner and outer nanoshells determines the resonant frequencies of the multilayer nanostructure.

A hybridization model for the plasmon response of complex nanostructures.

This feature article highlights work from the authors' laboratories on the synthesis, assembly, reactivity, and optical applications of metallic nanoparticles of nonspherical shape, especially nanorods. The synthesis is a seed-mediated growth procedure, in which metal salts are reduced initially with a strong reducing agent, in water, to produce ∼4 nm seed particles. Subsequent reduction of more metal salt with a weak reducing agent, in the presence of structure-directing additives, leads to the controlled formation of nanorods of specified aspect ratio and can also yield other shapes of nanoparticles (stars, tetrapods, blocks, cubes, etc.). Variations in reaction conditions and crystallographic analysis of gold nanorods have led to insight into the growth mechanism of these materials. Assembly of nanorods can be driven by simple evaporation from solution or by rational design with molecular-scale connectors. Short nanorods appear to be more chemically reactive than long nanorods. Finally, optical applica...

Anisotropic metal nanoparticles: Synthesis, assembly, and optical applications

The optical response of ring-shaped gold nanoparticles prepared by colloidal lithography is investigated. Compared to solid gold particles of similar size, nanorings exhibit a redshifted localized surface plasmon that can be tuned over an extended wavelength range by varying the ratio of the ring thickness to its radius. The measured wavelength variation is well reproduced by numerical calculations and interpreted as originating from coupling of dipolar modes at the inner and outer surfaces of the nanorings. The electric field associated with these plasmons exhibits uniform enhancement and polarization in the ring cavity, suggesting applications in near-infrared surface-enhanced spectroscopy and sensing.

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Optical properties of gold nanorings

The optical properties of gold nanodisk arrays prepared by colloidal lithography are studied experimentally. The arrays exhibit short range translational order and weak interparticle interactions. Tunable localized surface plasmon resonances are achieved by varying the diameter of the disks at constant disk height. The macroscopic optical properties are well-described by modeling the gold disks as oblate spheroids in the electrostatic limit. The optical sensing capabilities of the disks are investigated by varying the surrounding refractive index. It is found, in agreement with theory, that more oblate disk shapes have higher sensitivity. This suggests that nanodisks prepared by colloidal lithography are of interest as substrates for optimizing optical biosensing methods at the nanometer scale.

Optical Properties of Short Range Ordered Arrays of Nanometer Gold Disks Prepared by Colloidal Lithography

Control of nanoparticle film structure for colloidal lithography

Elastic scattering measurements show that isolated nanometric holes in optically thin Au films exhibit a localized surface plasmon resonance in the red to near-infrared region. The hole plasmon red shifts with increasing hole diameter or increasing refractive index of the surrounding medium, analogous to a dipolar particle plasmon. A pronounced blue shift is observed when the distance between holes is decreased, indicating an enhanced coupling between holes mediated by surface plasmon polaritons of the intervening flat film surface.

Optical Spectroscopy of Nanometric Holes in Thin Gold Films

To evaluate the influence of substratum surface characteristics on protein adsorption processes, we have investigated the adsorption (adsorbed amount, supramolecular organization) of collagen on model substrata exhibiting controlled topography and surface chemistry. Substrata were prepared in two steps: (i) gold deposition onto silicon wafers (smooth substrata) and onto a support with nanoscale protrusions created by colloidal lithography (rough substrata); (ii) functionalization with CH3 (hydrophobic) and OH (hydrophilic) groups, using alkanethiol self-assembly. Atomic force microscopy (AFM) images were recorded under water, prior to and after collagen adsorption, and the images were analyzed quantitatively using two independent approaches. On smooth substrata, collagen formed a similar to6 nm thick, homogeneous layer with low roughness on hydrophilic surfaces, and a similar to20 nm thick layer exhibiting elongated aggregated structures on hydrophobic surfaces. Film thickness measurements (AFM) together with X-ray photoelectron spectroscopy (XPS) revealed larger adsorbed amounts on hydrophobic surfaces compared to hydrophilic ones. On rough substrata, the adsorbed amounts were similar to those found on smooth substrata; however, the collagen molecules no longer formed aggregated structures on the hydrophobic surfaces. It is concluded that while the adsorbed amount is only affected by the surface chemistry, the supramolecular organization of the adsorbed layer is controlled both by surface chemistry and topography. The approach presented here will have great value in biophysics for investigating bioadsorption and bioadhesion processes on substrata of defined surface properties.

Per Hanarp

Papers

Optical properties of gold nanorings

Optical Properties of Short Range Ordered Arrays of Nanometer Gold Disks Prepared by Colloidal Lithography

Control of nanoparticle film structure for colloidal lithography

Optical Spectroscopy of Nanometric Holes in Thin Gold Films

Protein Adsorption on Model Surfaces with Controlled Nanotopography and Chemistry