Polyelectrolyte/gold nanoparticle multilayers composed of poly(L-lysine) (pLys) and mercaptosuccinic acid (MSA) stabilized gold nanoparticles (Au NPs) were built up using the electrostatic layer-by-layer self-assembly technique upon a gold electrode modified with a first layer of MSA. The assemblies were characterized using UV-vis absorption spectroscopy, cyclic and square-wave voltammetry, electrochemical impedance spectroscopy, and atomic force microscopy. Charge transport through the multilayer was studied experimentally as well as theoretically by using two different redox pairs [Fe(CN) 6 ] 3-/4-and [Ru(NH 3 ) 6 ] 3+/2+ . This paper reports a large sensitivity to the charge of the outermost layer for the permeability of these assemblies to the probe ions. With the former redox pair, dramatic changes in the impedance response were obtained for thin multilayers each time a new layer was deposited. In the latter case, the multilayer behaves as a conductor exhibiting a strikingly lower impedance response, the electric current being enhanced as more layers are added for Au NP terminated multilayers. These results are interpreted quite satisfactorily by means of a capillary membrane model that encompasses the wide variety of behaviors observed. It is concluded that nonlinear slow diffusion through defects (pinholes) in the multilayer is the governing mechanism for the [Fe(CN) 6 ] 3-/4-species, whereas electron transfer through the Au NPs is the dominant mechanism in the case of the [Ru(NH 3 ) 6 ] 3+/2+ pair.

Gold nanowire networks (AuNWNs) with average widths of 17.74 nm (AuNWN(1)) or 23.54 nm (AuNWN(2)) were synthesized by direct reduction of HAuCl(4) with sodium borohydride powder in deep eutectic solvents, such as ethaline or reline, at 40 °C. Their width and length were dependent on the type of solvent and the NaBH(4)/HAuCl(4) molar ratio (32 in ethaline and 5.2 in reline). High resolution transmission electron microscopy (HR-TEM) analysis of the gold nanowire networks showed clear lattice fringes of polycrystalline nanopowder of d = 2.36, 2.04, 1.44, and 1.23 Å corresponding to the (111), (200), (220), or (311) crystallographic planes of face centered cubic gold. The purified AuNWNs were used as catalysts for the chemical reduction of p-nitroaniline to diaminophenylene with sodium borohydride in aqueous solution. The reaction was monitored in real time by UV-vis spectroscopy. The results show that the reduction process is six times faster in the presence of gold nanowire networks stabilized by urea from the reline (AuNWN(2)) than in the presence of gold nanowire networks stabilized by ethylene glycol from ethaline (AuNWN(1)). This is due to a higher number of corners and edges on the gold nanowires synthesized in reline than on those synthesized in ethaline as proven by X-ray diffraction (XRD) patterns recorded for both types of gold nanowire networks. Nevertheless, both types of nanomaterials determined short times of reaction and high conversion of p-nitroaniline to diaminophenylene. These gold nanomaterials represent a new addition to a new generation of catalysts: gold based catalysts.

Multilayer films composed of poly(l-arginine) (pArg) and mercaptoundecanoic acid (MUA) stabilized gold nanoparticles (Au−MUA NPs) have been fabricated based on the electrostatic layer-by-layer self-assembly technique upon a gold electrode modified with a first layer of mercaptosuccinic acid (MSA). The formation of the pArg/Au−MUA NP self-assemblies as alternative multilayers was confirmed by UV−vis absorption spectroscopy and atomic force microscopy while their electrochemical properties were studied using cyclic voltammetry, square wave voltammetry, and electrochemical impedance spectroscopy. Charge transport through the multilayer was studied experimentally by using the redox pair [Fe(CN)6]3-/4-. It was found that these new assemblies have a high permeability to the probe ions. The presence of the Au−MUA NPs greatly improves the conductivity and the electron-transfer ability of the film which exhibited new electrical properties characterized by a low impedance response and enhanced electric current as more layers were added for both Au−MUA NP and pArg terminated multilayers. It is concluded that the behavior observed is based on two cumulative contributions:  electron transfer mediated by the Au−MUA NPs layers and ionic diffusion favored by the poly(l-arginine) layers due to the Donnan inclusion. The films obtained showed high conductive properties which represent very promising features for the construction of electrochemical sensors or nanoelectronic devices.

Herein we describe the synthesis of water-soluble platinum nanodendrites in dimethylformamide (DMF), in the presence of polyethyleneimine (PEI) as a stabilizing agent. The average size of the dendrites is in the range of 20-25 nm while their porosity can be tuned by modifying the concentration of the metal precursor. Electron tomography revealed different crystalline orientations of nanocrystallites in the nanodendrites and allowed a better understanding of their peculiar branching and porosity. The high surface area of the dendrites (up to 22 m(2) g(-1)) was confirmed by BET measurements, while X-ray diffraction confirmed the abundance of high-index facets in the face-centered-cubic crystal structure of Pt. The prepared nanodendrites exhibit excellent performance in the electrocatalytic oxidation of ethanol in alkaline solution. Sensing, selectivity, cycleability and great tolerance toward poisoning were demonstrated by cyclic voltammetry measurements.

We report the electrodeposition of metallic silver onto gold nanostars adsorbed to ITO electrodes. The electrochemical process was studied at the single particle level by correlated in situ dark field spectroscopy and scanning electron microscopy (SEM). Underpotential deposition avoids bulk silver formation on the ITO substrates. SEM proves that deposition occurs on all surfaces of the gold nanostars when polyvinylpyrrolidone (PVP) is stabilizing the nanostars or preferentially at the nanostar tips when the ligand is removed. The surface plasmon resonance blue-shifts by more than 100 nm following the formation of a 5 nm Ag film on PVP stabilized gold nanostars, moving the scattered color from the near-infrared to red or orange. The spectral shifts can be accurately modeled using finite element simulations. These results demonstrate that the morphology and composition of individual bimetallic nanocrystals can be engineered electrochemically.

Electrochemical properties of Au electrodes sequentially modified by self-assembled 1,6 hexanedithiol (1,6HDT) and gold nanorods (AuNRs) are investigated by cyclic voltammetry, square-wave voltammetry, and electrochemical impedance spectroscopy, using [Fe(CN) 6 ] 3-/4-as redox probes. The nanorods stabilized by cetyltrimetylammonium bromide (CTAB) with aspect ratios of 2.20, 2.80, and 3.77 were grown by a seedmediated procedure and chemically bonded to the 1,6HDT-coated electrodes by a place exchange reaction at a 27°C solution temperature. Topographic tapping mode atomic force microscopy measurements revealed an end bonding of the 2.20 aspect ratio rods and a side surface bonding of the 2.80 and 2.77 aspect ratio rods. Analysis of the electrochemical responses as a function of the sizes and surface orientations of the rods revealed that the electron transfer is faster at electrodes modified with smaller and vertically aligned nanorods than those modified with larger and randomly attached nanorods (side surface bonding). A progressive increase in the charge transfer resistance R CT from bilayers composed of 1,6HDT and 2.20 aspect ratio rods to bilayers composed of 1,6HDT and rods of 2.80 or 3.77 aspect ratios was described by a tunneling parameter of ) 1.07 per thiol chain unit. This behavior suggests that the electron transfer kinetics is controlled by coherent electron tunneling across the 1,6HDT monolayer. In addition, the several orders of magnitude changes of the apparent charge transfer resistance upon nanorod adsorption suggest a charging of the rods by the redox probes in solution and electron transfer across them. It is concluded that the electron transfer proceeds via a three-step process: charging of the rods by the redox probes in solution, electron transport across the rods, and electron tunneling across the 1,6HDT-SAM toward the underlying Au substrates.

Gold nanorods (AuNRs) with an aspect ratio of 2.33 or 3.16 were self-assembled onto 1,6-hexanedithiolmodified gold electrodes based on covalent interaction at a solution temperature of 35°C. The formation of the 1,6HDT/AuNR bilayers as a function of the nanorods' adsorption time was studied by atomic force microscopy and quartz crystal microbalance, whereas their physical properties and chemical bonding were studied by contact angle and FT-IRRAS spectroscopy measurements. It was found that both types of nanorods were covalently bonded to the Au-1,6HDT-SAM modified electrodes in an end topography and with a high surface density. The electrochemical properties of the Au-1,6HDT-AuNR modified electrodes, as a function of the nanorods' adsorption time, were studied by cyclic voltammetry, square wave voltammetry, and electrochemical impedance spectroscopy using [Fe(CN) 6 ] 3-/4-as the redox probes. The highest enhancement of the electrical current in the cyclic voltammograms was recorded at the Au-1,6HDT-AuNR modified electrodes for 7 h of chemisorption of 2.33 aspect ratio rods or 15 h of chemisorption of 3.16 aspect ratio rods. The high decrease of the apparent charge-transfer resistance upon nanorod self-assembly suggests a charging of the rods by the [Fe(CN) 6 ] 3-/4-in solution and electron transfer across them. Moreover, the variation of the tunneling parameter suggests that the electron tunneling process through the 1,6HDT molecules is more efficient at the electrodes modified with bilayers containing short rods ( ) 0.78 ( 0.08 Å -1 /per methylene unit) than at the electrodes modified with bilayers containing long rods ( ) 0.84 ( 0.10 Å -1 /per methylene unit). The self-assembly of the AuNRs in an end-bonding topography with a high surface coverage restored almost completely the electronic communication that was entirely blocked by the preceding 1,6HDT layer.

The build up and electrochemical characterization of interfacial composite nanostructures containing a cationic polyelectrolyte and negatively charged mercaptosuccinic acid stabilized gold nanoparticles (AuNPs) is reported. The nanostructures were formed at the interface between two immiscible electrolyte solutions in which the organic phase is an immobilized 2-nitrophenyl octyl ether/PVC gel. The growth of the multilayer was verified with UV-vis spectra, and approximately a linear increase in UV-vis absorbance with increasing number of layers was observed. The interfacial capacitance of the multilayers was measured as a function of the potential and a theoretical model was developed to explain the results. The excellent agreement between theoretical and experimental capacitance curves allows us to conclude that nanocomposites behave similarly to polyelectrolyte multilayers, with the outmost layer determining the alternating sign of the outer surface charge density. Cyclic voltammograms were used to evaluate the transfer rate constant across the multilayers of a model drug, metoprolol, and the standard probe tetraethylammonium cation. The apparent rate constants were slightly larger than in other studies in the literature and decrease with the increasing number of layers.