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.

Nanomaterials are engineered structures with at least one dimension of 100 nanometers or less. These materials are increasingly being used for commercial purposes such as fillers, opacifiers, catalysts, semiconductors, cosmetics, microelectronics, and drug carriers. Materials in this size range may approach the length scale at which some specific physical or chemical interactions with their environment can occur. As a result, their properties differ substantially from those bulk materials of the same composition, allowing them to perform exceptional feats of conductivity, reactivity, and optical sensitivity. Possible undesirable results of these capabilities are harmful interactions with biological systems and the environment, with the potential to generate toxicity. The establishment of principles and test procedures to ensure safe manufacture and use of nanomaterials in the marketplace is urgently required and achievable.

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Toxic Potential of Materials at the Nanolevel

Synthesis and surface engineering of iron oxide nanoparticles for biomedical applications

Rapid growth in nanotechnology is increasing the likelihood of engineered nanomaterials coming into contact with humans and the environment. Nanoparticles interacting with proteins, membranes, cells, DNA and organelles establish a series of nanoparticle/biological interfaces that depend on colloidal forces as well as dynamic biophysicochemical interactions. These interactions lead to the formation of protein coronas, particle wrapping, intracellular uptake and biocatalytic processes that could have biocompatible or bioadverse outcomes. For their part, the biomolecules may induce phase transformations, free energy releases, restructuring and dissolution at the nanomaterial surface. Probing these various interfaces allows the development of predictive relationships between structure and activity that are determined by nanomaterial properties such as size, shape, surface chemistry, roughness and surface coatings. This knowledge is important from the perspective of safe use of nanomaterials.

Understanding biophysicochemical interactions at the nano–bio interface

http://sistemas.eel.usp.br/docentes/arquivos/2166002/1234Nb/Geetha-review2009.pdf

Ti based biomaterials, the ultimate choice for orthopaedic implants – A review

A flash CVD process can be employed to grow micron- and nano-sized tree-like structures, particularly carbon structures on graphite electrodes. This process involves fast cyclic resistive heating of electrodes in an atmosphere of inert gas and hydrocarbons at below atmospheric pressure.

Carbon nanotrees formed by flash CVD method

In vitro evaluation of novel polymer/ceramic nanocomposites for orthopaedic material applications

: The present study was motivated by the need for accurately-controlled and well-characterized novel biomaterial formulations for the study of cell-protein-material interactions. For this purpose, the current research has focused on the design, fabrication and characterization of model native oxide-coated silicon surfaces decorated with silica nanoparticles of select sizes, and has examined the adhesion of osteoblasts and fibroblasts on these nanoparticle-decorated surfaces. The results demonstrate the capability to deposit nanoparticles of select diameters and substrate surface coverage onto native silicon oxide-coated silicon, the firm attachment of these nanoparticles to the underlying native silicon oxide, and that nanoparticle size and coverage modulate adhesion of osteoblasts and fibroblasts to these substrates. The material formulations tested provide a well-controlled and well-characterized set of model substrates needed to study the effects of nanoscale features on the functions of cells that are critical to the clinical fate of implantable biomaterials.

Nanoparticle-Decorated Surfaces for the Study of Cell-Protein-Substrate Interactions

Nanoparticle-loaded encapsulants provide unique optical and material properties for the enhancement of light extraction efficiency in light-emitting diodes (LEDs). We report on the uniform dispersion of TiO2 nanoparticles with average diameter of 40 nm in epoxy, and the demonstration of a refractive index (n)of 1.68 at 400 nm wavelength, higher than that of pure epoxy (n = 1.53). It is found that proper chemical surfactants and nanoparticle preparation are critical to eliminate agglomeration of nanoparticles. Theoretical analysis of optical scattering in nanoparticle-loaded encapsulation materials reveals that although the size and loading factor of nanoparticles greatly influence scattering, specular transparency of the encapsulant film occurs if the thicknesses of the films are kept below the optical scattering length. Furthermore, the encapsulants benefit from an optimized scattering coefficient as demonstrated by three-dimensional ray-tracing simulations showing light extraction efficiency enhancements greater than 50%.

https://www.cambridge.org/core/services/aop-cambridge-core/content/view/S1946427400050892

Nanoparticle-loaded encapsulation materials for light-emitting diode applications

Provided is a gold nanocage with pores, charged ligand molecules covalently bound to internal surfaces of the gold nanocage, and payload molecules electrostatically adsorbed onto said charged ligand molecules, wherein a pore diameter is between 1.2 and 20 times a gyration radius of the payload molecule. Also provided is a method for making a nanoparticle, including using polyvinylpyrrolidone as a capping agent in a galvanic replacement reaction to convert a silver nanocube into a gold nanocage having pores, replacing the polyvinylpyrrolidone on internal surfaces with charged ligand molecules, and electrostatically adsorbing payload molecules onto the charged ligand molecules, with a pore diameter less than twenty times a gyration radius of the payload molecule. Also provided is a method of delivering a pharmacological agent to a mammalian cell, including contacting the cell with a gold nanocage having pores, ligand molecules bound to internal surfaces, and pharmacological agent adsorbed onto ligand molecules.

Richard W. Siegel

Papers

Carbon nanotrees formed by flash CVD method

In vitro evaluation of novel polymer/ceramic nanocomposites for orthopaedic material applications

Nanoparticle-Decorated Surfaces for the Study of Cell-Protein-Substrate Interactions

Nanoparticle-loaded encapsulation materials for light-emitting diode applications

Internalization of proteins into hollowed gold nanostructures