Assembly of polystyrene-coated gold nanoparticles at the air-water interface.

Gold nanoparticles (NPs) coated with thiol-terminated polystyrene chains of varying molar mass were added to polystyrene-b-polymethylmethacrylate (PS-b-PMMA) block copolymer monolayers at the air-water interface. Composite films were transferred to solid substrates by the Langmuir-Blodgett technique. For most of the investigated systems, TEM micrographs and AFM images reveal the formation of 2D island-like aggregates of particles organized on a close-packed hexagonal lattice. This characteristic aggregate formation is lost when PS ligands are within the same length regime as the PS block from the copolymer. The results are compared with those obtained for analogous systems containing no copolymer where NPs are deposited on either a bare water surface or bare glass. Interparticle distance between NPs is found to depend on the surface on which they are deposited, the presence or not of the copolymer monolayer, and ligand length.

Plasmonic nanopipette biosensor.

Integrating a SERS immunoassay on a plasmonic "patch clamp" nanopipette enabled nanobiosensing for the detection of IgG. A SERS response was obtained using a sandwich assay benefiting from plasmon coupling between a capture Au nanoparticle (AuNP) on a nanotip and a second AuNP modified with a Raman active reporter and an antibody selective for IgG. The impact of nanoparticle shape and surface coverage was investigated alongside the choice of Raman active reporter, deposition pH, and plasmonic coupling, in an attempt to fully understand the plasmonic properties of nanopipettes and to optimize the nanobiosensor for the detection of IgG. These probes will find applications in various fields due to their nanoscale size leading to the possibility of spatially and temporally addressing their location near cells to monitor secretion of biomolecules.

Single step synthesis and organization of gold colloids assisted by copolymer templates.

We report here an original single-step process for the synthesis and self-organization of gold colloids by simply incorporating gold salts into a solution prepared using polystyrene (PS)-polymethylmethacrylate copolymer and thiolated PS with propylene glycol methyl ether acetate as a solvent. The spin-coating and annealing of this solution then allows the formation of PS domains. Depending on the polymer concentration of the as-prepared solution, there can be either one or several gold nanoparticles (Au NPs) per PS domain. For high concentrations of Au NPs in PS domains, the coupling between plasmonic NPs leads to the observation of a second peak in the optical extinction spectrum. Such a collective effect could be relevant for the development of optical strain sensors in the near future.

Nanostructured carbon beads--properties and biomedical applications.

In this study, amorphous carbonaceous nanoparticles were prepared by a simple hydrothermal process using glucose as precursor. The nearly perfect spherical particles (beads) with the dimensions in the range of 10-500 nm were obtained depending on the main process parameters (precursor concentration, temperature, and time). The particles size, surface morphology, structure, and composition have been examined by TEM, SEM, X-ray diffraction, XPS, FTIR and Raman spectroscopy. These amorphous carbonaceous nanobeads (a-CNBs) have been found nontoxic in vitro with a variety of cultured cell lines. The size-dependent effect of a-CNBs addition on cell function has been observed. For example, a-CNBs can, in some cases, substantially increase interleukin-12 (IL-12) production by bone marrow dendritic cells. It has been further demonstrated that a-CNBs can be modified with fluorescent dye molecules or loaded with anti-cancer drugs for bioimaging or therapeutic purposes, respectively. The results of these tests and the strategies for the particle preparation and functionalization for biomedical applications have been discussed.

Two-dimensional self-organization of polystyrene-capped gold nanoparticles.

Thiol end-functionalized polystyrene chains have been introduced onto the surface of gold nanoparticles via a two-step grafting-to method. This simple grafting procedure is demonstrated to be efficient for gold nanoparticles of different sizes and for particles initially dispersed in either aqueous or organic media. The method has been applied successfully for a relatively large range of polystyrene chain lengths. Grafting densities, as determined by thermogravimetric analysis, are found to decrease with increasing chain length. In all cases, the grafting density indicates a dense brush conformation for the tethered chains. The resulting functionalized nanoparticles self-organize into hexagonally ordered monolayers when cast onto solid substrates from chloroform solution. Furthermore, the distance between the gold cores in the dried monolayer is controlled by the molecular weight of the grafted polystyrene. Optical absorption spectra recorded for the organized monolayers show the characteristic plasmon absorption of the gold particles. Importantly, the plasmon resonance frequency exhibits a distinct dependence on interparticle separation that can be attributed to plasmon coupling between neighboring gold cores.

Synthesis of complex shape gold nanoparticles in water-methanol mixtures.

Gold nanoparticles with shapes which varied from spheres to multipods and polygons were prepared with a seedless approach in water/methanol mixtures in the presence of polyvinyl alcohol using sodium ascorbate as the reducing agent. The shape of Au nanoparticles is critically affected by the water/methanol ratio, as well as by the ratio of hydrogen tetrachloroaurate (HAuCl4) to sodium ascorbate and the concentration of HAuCl4 in the reaction mixture. A decreased ratio of water to methanol below 30/70 leads to the formation of multi-branched nanoparticles with the size in the range of 30-70 nm at relatively low HAuCl4 concentration, whereas polygons are formed when HAuCl4 concentration increases. The polyvinyl alcohol stabilized multi-branched Au nanoparticle colloids were stable at room temperature for a period of at least six-month.

Optical tests of nanoengineered liquid mirrors.

We describe a new technology for the fabrication of inexpensive high-quality mirrors. We begin by chemically producing a large number of metallic nanoparticles coated with organic ligands. The partides are then spread on a liquid substrate where they self-assemble to give optical quality reflective surfaces. Since liquid surface can be modified by a variety of means (e.g., rotation, electromagnetic fields), this opens the possibility of making a new class of versatile and inexpensive optical elements that can have complex shapes and that can be modified within short time scales. Interferommetric measurements show optical quality surfaces. We have obtained reflectivity curves that show 80% peak reflectivities. We are confident that we can improve the reflectivity curves because theoretical models predict higher values. We expect nanoengineered liquid mirrors to be useful for scientific and engineering applications. The technology is interesting for large optics, such as large rotating parabolic mirrors, because of its low cost. Furthermore, because the surfaces of of ferrofluids can be shaped with magnetic fields, one can generate complex, time-varying surfaces that are difficult to make with conventional techniques.