We report an efficient synthesis of copper indium sulfide nanocrystals with strong photoluminescence in the visible to near-infrared. This method can produce gram quantities of material with a chemical yield in excess of 90% with minimal solvent waste. The overgrowth of as-prepared nanocrystals with a few monolayers of CdS or ZnS increases the photoluminescence quantum efficiency to > 80%. On the basis of time-resolved spectroscopic studies of core/shell particles, we conclude that the emission is due to an optical transition that couples a quantized electron state to a localized hole state, which is most likely associated with an internal defect.

Gold nanorods have received much attention due to their unique optical and electronic properties which are dependent on their shape, size, and aspect ratio. This article covers in detail the synthesis, functionalization, selfassembly, and sensing applications of gold nanorods. The synthesis of three major types of rods is discussed: single-crystalline and pentahedrally-twinned rods, which are synthesized by wet chemistry methods, and polycrystalline rods, which are synthesized by templated deposition. Functionalization of these rods is usually necessary for their applications, but can often be problematic due to their surfactant coating. Thus, general strategies are provided for the covalent and noncovalent functionalization of gold nanorods. The review will then examine the signifi cant progress that has been made in controllable assembly of nanorods into various arrangements. This assembly can have a large effect on measurable properties of rods, making it particularly applicable towards sensing of a variety of analytes. Other types of sensing not dependent on nanorod assembly, such as refractive-index based sensing, are also discussed.Adv.

Highly organized supercrystals of Au nanorods with plasmonic antennae enhancement of electrical field have made possible fast direct detection of prions in complex biological media such as serum and blood. The nearly perfect three-dimensional organization of nanorods render these systems excellent surface enhanced Raman scattering spectroscopy substrates with uniform electric field enhancement, leading to reproducibly high enhancement factor in the desirable spectral range.S urface enhanced Raman scattering (SERS) spectroscopy is not only one of the most sensitive analytical techniques but also can be used under biological conditions. Additionally, SERS signals are strongly dependent on conformational changes in macromolecules such as proteins (1). Unfortunately, although SERS of proteins has been consistently investigated during the last decade (2-6), enhancement factors (EFs) obtained for most conventional (nonfluorescent) proteins are still insufficient for their direct detection in complex biological media (7). There are two additional very serious challenges as well. Both quantitative detection by SERS and reproducible geometry of the "hot spots" necessary for SERS are difficult to achieve. The way to solve these challenges is to design and fabricate a highly organized photonic structure (8) that provides a high electromagnetic field enhancement in a reproducible geometry (9, 10). Recent demonstration of near-field focalization by nanoantennas (11,12) has paved the way for development of ultrasensitive SERS substrates that can concentrate the near field within certain confined regions, allowing one to obtain extremely high EFs (13-15). Such a nanoantenna effect was predicted and found for nanorod (NR) dimers, where the maximum focalization is present at the NR tips (16,17). One can hypothesize, therefore, that a highly organized system of NRs (18-21) acting as an extended nanoantenna may provide resolution for the SERS challenges of proteins or their segments. In turn, this hypothesis can lead to significant technological development for relevant biomedical problems. One example of those problems is the presymptomatic detection of scrambled prions directly in biological fluids.Prions are hard-to-detect infectious agents that cause a number of fatal neurodegenerative diseases in mammalians such as bovine spongiform encephalopathy (BSE), scrapie of sheep, and Creutzfeldt-Jakob disease (CJD) of humans (22), and recently traced as well to other neurodegenerative syndromes as Alzheimer's (23) and Parkinson (24). Invariably, all of these diseases involve the modification of the endogenous and functional prion protein (PrP C ) into a nonfunctional but much more stable form (PrP SC ) giving rise to the so-called amyloid plaques in the brain and other nervous tissues (25). Detection of its presence for contention in cattle or diagnosis in humans or blood transfusion banks (26) is very difficult even by state-of-the-art immunological methods such as fluorescence immunoassay, RIA, or ELISA (27) or protein misfolding c...

Here we describe the first example of 2 nm gold nanoparticles (Au NPs) covalently functionalized with a chemotherapeutic drug, paclitaxel. The synthetic strategy involves the attachment of a flexible hexaethylene glycol linker at the C-7 position of paclitaxel followed by coupling of the resulting linear analogue to phenol-terminated gold nanocrystals. The reaction proceeds under mild esterification conditions and yields the product with a high molecular weight, while exhibiting an extremely low polydispersity index (1.02, relative to linear polystyrene standards). TGA analysis of the hybrid nanoparticles reveals the content of the covalently attached organic shell as nearly 67% by weight, which corresponds to approximately 70 molecules of paclitaxel per 1 nanoparticle. The presence of a paclitaxel shell with a high grafting density renders the product soluble in organic solvents and allows for detailed (1)H NMR analysis and, therefore, definitive confirmation of its chemical structure. High-resolution TEM was employed for direct visualization of the inorganic core of hybrid nanoparticles, which were found to retain their average size, shape, and high crystallinity after multiple synthetic steps and purifications. The interparticle distance substantially increases after the attachment of paclitaxel as revealed by low-magnification TEM, suggesting the presence of a larger organic shell. The method described here demonstrates that organic molecules with exceedingly complex structures can be covalently attached to gold nanocrystals in a controlled manner and fully characterized by traditional analytical techniques. In addition, this approach gives a rare opportunity to prepare hybrid particles with a well-defined amount of drug and offers a new alternative for the design of nanosized drug-delivery systems.

Ring‐a‐ring o'rods: Hybrid gold/polymer core–shell nanorods spontaneously organize into ringlike arrays when a drop of their solution is dried on a substrate. The process is highly reproducible and generates thousands of well‐defined rings of nanorods in a matter of seconds (see TEM image). Studies revealed that water droplets, which condense on the surface of nonpolar solvents, template the formation of the rings.

Recent advances in chemical synthesis have made it possible to produce gold and silver nanowires that are free of large-scale crystalline defects and surface roughness. Surface plasmons can propagate along the wires, allowing them to serve as optical waveguides with cross sections much smaller than the optical wavelength. Gold nanowires provide improved chemical stability as compared to silver nanowires, but at the cost of higher losses for the propagating plasmons. In order to characterize this trade-off, we measured the propagation length and group velocity of plasmons in both gold and silver nanowires. Propagation lengths are measured by fluorescence imaging of the plasmonic near fields. Group velocities are deduced from the spacing of fringes in the spectrum of coherent light transmitted by the wires. In contrast to previous work, we interpret these fringes as arising from a far-field interference effect. The measured propagation characteristics agree with numerical simulations, indicating that propagation in these wires is dominated by the material properties of the metals, with additional losses due to scattering from roughness or grain boundaries providing at most a minor contribution. The propagation lengths and group velocities can also be described by a simple analytical model that considers only the lowest-order waveguide mode in a solid metal cylinder, showing that this single mode dominates in real nanowires. Comparison between experiments and theory indicates that widely used tabulated values for dielectric functions provide a good description of plasmons in gold nanowires but significantly overestimate plasmon losses in silver nanowires.

Because physical and chemical properties of nanostructures strongly depend on their shape, it is of great importance to find either synthetic or separation techniques that can produce objects of a particular shape in a pure state. This manuscript describes a solution to a long standing problem of separating 2D platelets from 1D nanorods. The key aspect of our approach relies on the partial dissolution of faceted platelets with Au(III)/CTAB complex that transforms them into smaller nanodisks. Because of the reduction in size, the 2D structures become fully soluble in water and can be separated from the nanorods that undergo slow precipitation. In addition, the isolated nanodisks can be converted back into initial faceted platelets upon treatment with Au(I)/ascorbic acid mixture. As a result of these simple procedures, a seemingly inseparable mixture of rods, platelets, and spheres is converted into nearly pure individual components.

We report ultrathin pH-responsive plasmonic membranes of [poly(methacrylic acid)-gold nanorods] 20 (PMAA-Au NRs) 20 with gold nanorods embedded into swollen cross-linked LbL hydrogels. In contrast to the most of known pH responsive materials which rely on pH-triggered change in the intensity of photoluminescence or plasmon bands, the responsive structures suggested here exhibit a significant pHtriggered shift in easily detectable, strong plasmon resonance band. We show that a pH-induced deswelling of the (PMAA-Au NRs) 20 hydrogel film in the pH change from 8 to 5 causes a dramatic blue-shift of the longitudinal plasmon peak by 21 nm due to the increased side-by-side interactions of adjacent gold nanorods. These composite hydrogel multilayer films can be released from the substrates yielding freefloating and optically pH-responsive ultrathin hydrogel films which can be transferred to the appropriate solid substrates.