Films of monolayer protected Au clusters (MPCs) with mixed alkanethiolate and omega-carboxylate alkanethiolate monolayers, linked together in a network polymer by carboxylate-Cu2+-carboxylate bridges, exhibit electronic conductivities (sigma(EL)) that vary with both the numbers of methylene segments in the ligands and the bathing medium (N2, liquid or vapor). A chainlength-dependent swelling/contraction of the film's internal structure is shown to account for changes in sigma(EL). The linker chains appear to have sufficient flexibility to collapse and fold with varied degrees of film swelling or dryness. Conductivity is most influenced (exponentially dependent) by the chainlength of the nonlinker (alkanethiolate) ligands, a result consistent with electron tunneling through the alkanethiolate chains and nonbonded contacts between those chains on individual, adjacent MPCs. The sigma(EL) results concur with the behavior of UV-vis surface plasmon adsorption bands, which are enhanced for short nonlinker ligands and when the films are dry. The film conductivities respond to exposure to organic vapors, decreasing in electronic conductivity and increasing in mass (quartz crystal microgravimetry, QCM). In the presence of organic vapor, the flexible network of linked nanoparticles allows for a swelling-induced alteration in either length or chemical nature of electron tunneling pathways or both.

Here we quantify the electrochemical oxidation of Ag nanoparticles (NPs) as a function of size by electrostatically attaching Ag NPs synthesized by seed-mediated growth in the presence of citrate (diameter = 8 to 50 nm) to amine-functionalized indium-tin oxide coated glass electrodes (Glass/ITO), obtaining a linear sweep voltammogram from 0.1 V, where Ag(0) is stable, up to 1.0 V, and observing the peak potential (E(p)) for oxidation of Ag(0) to Ag(+). Electrostatic attachment to the organic linker presumably removes direct interactions between Ag and ITO and allows control over the total Ag coverage by altering the soaking time. This is important as both metal-electrode interactions and overall Ag coverage can affect E(p). E(p) shifts positive from an average of 275 to 382 mV as the Ag NP diameter increases for a constant Ag coverage and under conditions of planar diffusion, suggesting a shift in E(p) due to a thermodynamic shift in E(0) for the Ag/Ag(+) redox couple with size. The negative shift in E(p) with decreasing Ag NP radius follows the general trend predicted by theory and agrees with previous qualitative experimental observations. A better understanding of metal nanostructure oxidation is crucial considering their potential use in many different applications and the importance of metal corrosion processes at the nanoscale.

Electrochemistry, FTIR-external reflection spectroscopy (FTIR-ERS), and scanning tunneling microscopy (STM) were used to study the ability of n-alkanethiol self-assembled monolayers (SAMs) to protect Au from corrosion in aqueous Br- solutions. The thickness and terminal functional group of the SAMs were varied to determine which factors lead to the greatest corrosion passivation. SAMs prepared on Au from the following molecules were studied:  HS(CH2)15CH3, HS(CH2)11CH3, HS(CH2)10COOH, and HS(CH2)11OH. The data reveal that, prior to corrosion, the SAMs are crystalline and highly ordered but that afterward they are disordered and oriented parallel to the surface plane. The results show that, for SAMs containing the same terminal functional group, corrosion resistance increases as the SAM thickness increases. For SAMs that are equal in thickness but contain different terminal functional groups, the end groups resulting in the most corrosion resistance follow the order OH > COOH > CH3. The hydrophilic SAM-modified Au surfaces corrode smoothly in a layer-by-layer fashion while the methyl-terminated, hydrophobic SAM-modified surfaces undergo localized corrosion (pitting). Since hydrophilic SAMs are generally more defective than methyl-terminated SAMs but provide the Au more protection, we conclude that initial SAM defectiveness is not a reliable predictor of its barrier properties.

There are a variety of methods for synthesizing or fabricating one-dimensional (1D) nanostructures containing heterojunctions between different materials. Here we review recent developments in the synthesis and fabrication of heterojunctions formed between different materials within the same 1D nanostructure or between different 1D nanostructures composed of different materials. Structures containing 1D nanoscale heterojunctions exhibit interesting chemistry as well as size, shape, and material-dependent properties that are unique when compared to single-component materials. This leads to new or enhanced properties or multifunctionality useful for a variety of applications in electronics, photonics, catalysis, and sensing, for example. This review separates the methods into vapor-phase synthesis, solution-phase synthesis, template-based synthesis, and other approaches, such as lithography, electrospinning, and assembly. These methods are used to form a variety of heterojunctions, including segmented, core/shell, branched, or crossed, from different combinations of semiconductor, metal, carbon, and polymeric materials.

The rate of electron self-exchange reactions between discretely charged metal-like cores of nanoparticles has been measured in multilayer films of nanoparticles by an electrochemical method. The nanoparticles are Au monolayer-protected clusters with mixed monolayers of hexanethiolate and mercaptoundecanoic acid ligands, linked to each other and to the Au electrode surface with carboxylate-metal ion-carboxylate bridges. Cyclic voltammetry of the nanoparticle films exhibits a series of well-defined peaks for the sequential, single-electron, double-layer charging of the 1.6-nm-diameter Au cores. The electron self-exchange is measured as a diffusion-like electron-hopping process, much as in previous studies of redox polymer films on electrodes. The average electron diffusion coefficient is DE = 10(+/-5) x 10(-8) cm2/s, with no discernible dependence on the state of charge of the nanoparticles or on whether the reaction increases or decreases the core charge. This diffusion constant corresponds to an average first-order rate constant kHOP of 2(+/-1) x 10(6) s(-1) and an average self-exchange rate constant, kEX, of 2(+/-1) x 10(8) M(-1) x s(-1), using a cubic lattice hopping model. This is a very large rate constant, considering the nominally lengthy linking bridge between the Au cores.