Redox-active π-conjugated organometallic monolayers: pronounced Coulomb blockade characteristic at room temperature.

We report the electrical transport characteristics of a series of molecular wires, fc-C≡C-C6H4-SAc (fc = ferrocenyl; Ac = acetyl) and AcS-C6H4-C≡C-(fc)n-C≡C-C6H4-SAc (n = 2, 3), consisting of multiple redox-active ferrocenyl centers. The self-assembled monolayers of these molecular wires on Au surfaces were comprehensively characterized by electrochemistry and conductive atomic force microscopy techniques. Characterization of the wires revealed that electron transport is made extremely efficient by the organometallic redox states. There is a strong electronic coupling between ferrocenyl moieties, and superior electron-transport ability exists through these semirigid molecular wires. Standard rate constants for the electron transfer between the electrode and the ferrocenyl moieties were measured for the monolayers by a potential-step chronoamperometry technique. The electron conduction through the molecular wires was estimated using the monolayers as a bridge from the Au(111) metal surface to the gold tip of a conductive atomic force microscope (CAFM). Using the CAFM, Coulomb blockade behavior arising from the capacitive charging of the multinuclear redox-active molecules was observed at room temperature. The conductance switching was mediated by the presence of various ferrocenyl redox states and each current step corresponded to a specific redox state.

Effect of nucleobase sequence on the proton-transfer reaction and stability of the guanine-cytosine base pair radical anion.

The formation of base pair radical anions is closely related to many fascinating research fields in biology and chemistry such as radiation damage to DNA and electron transport in DNA. However, the relevant knowledge so far mainly comes from studies on isolated base pair radical anions, and their behavior in the DNA environment is less understood. In this study, we focus on how the nucleobase sequence affects the properties of the guanine-cytosine (GC) base pair radical anion. The energetic barrier and reaction energy for the proton transfer along the N(1)(G)-H···N(3)(C) hydrogen bond and the stability of GC˙(-) (i.e., electron affinity of GC) embedded in different sequences of base-pair trimer were evaluated using density functional theory. The computational results demonstrated that the presence of neighboring base pairs has an important influence on the behavior of GC˙(-) in the gas phase. The excess electron was found to be localized on the embedded GC and the charge leakage to neighboring base pairs was very minor in all of the investigated sequences. Accordingly, the sequence behavior of the proton-transfer reaction and the stability of GC˙(-) is chiefly governed by electrostatic interactions with adjacent base pairs. However, the effect of base stacking, due to its electrostatic nature, is severely screened upon hydration, and thus, the sequence dependence of the properties of GC˙(-) in aqueous environment becomes relatively weak and less than that observed in the gas phase. The effect of geometry relaxation associated with neighboring base pairs as well as the possibility of proton transfer along the N(2)(G)-H···O(2)(C) channel have also been investigated. The implications of the present findings to the electron transport and radiation damage of DNA are discussed.

Constructions of silver nanowires and copper oxide microrings by a surface-formation technique.

We demonstrate a simple method to synthesize silver wires by thermal reduction of aqueous AgNO(3) droplet with catalytic anatase TiO(2) nanoparticles which were spin-coated on Si wafer. Structural characterization of the silver wires shows that the nanowires grow primarily along the [011] direction. SEM image of the silver wires clearly shows the catalytic TiO(2) nano-cluster attached to the end of the each silver wire. Since the process was surfactant-free, the silver nanowires prepared by our method retain the excellent electrical conductivity. The intrinsic resistivity calculated from the current-voltage curve for a wire with 12880.41 nm(2) cross-section area was 18.72 microohm cm, which is about 11.6 times higher than that of bulk silver (1.61 microohm cm). Our simple method can be also applied to generate CuO with ring-shaped microstructure by using ITO conducting glass as matrix. We have found that the size and reproducibility are well-controllable. A single phase of CuO ring-shaped microstructure with outer diameters ranging from approximately 13 to 17 microm and inner diameters ranging from approximately 1.4 to 3.3 microm was obtained. The composition of CuO microring was confirmed by thin-film XRD and XPS analyses.

One-step synthesis of uniform silver nanoparticles capped by saturated decanoate: direct spray printing ink to form metallic silver films.

The one-step synthesis and spectroscopic characterizations of size-controlled silver nanoparticles are described. The transmission electron microscopy (TEM), nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric-mass analysis (TGA-MS) and X-ray photoelectron spectroscopy (XPS) techniques were used to characterize the decanoate-protected silver nanoparticles. TEM analysis showed that spherical nanoclusters of 7.52 +/- 0.57 nm were produced. Furthermore, the particle sizes are uniform with a narrow size distribution. For all samples, Ag 3d(5/2) and 3d(3/2) components appeared at 368.5 and 374.5 eV, respectively, in the XPS spectrum; these values compare very well with the typical values of carboxylate-protected Ag nanoparticles. A thermal analysis mass spectrometer was used to analyze the desorption behavior of decanoate-protected nanoparticles. From the desorption maximum temperatures of 181 and 263 degrees C, activation energies of 27.2 and 32.2 kcal mol(-1) for the desorption processes in the Ag MPCs were obtained, assuming a first-order reaction and using a pre-exponential factor of 1 x 10(13) s(-1). A specific resistivity of 6.097 microOmega cm for the silver metal film (0.7 microm) on a Si wafer can be produced simply by thermal annealing of an Ag monolayer-protected clusters film under an atmosphere of 90% N(2)-10% H(2) at 300 degrees C for 1 h.

Characterization of pyridine-octanethiolated gold nanoparticles: desorption kinetics by thermal analysis mass spectrometry.

We describe a synthetic pathway to the formation of stable pyridine-functionalized octanethiolate mixed monolayer-protected Au clusters (MPCs). The spectroscopic characterization data of MPCs using NMR, UV-Vis, TEM, XPS, and thermal-analysis-mass techniques are discussed. TEM analysis showed that spherical nanoclusters of 3-5 nm were produced. Furthermore, the particle sizes are uniform with a narrow size distribution. The pyridine-functionalized MPCs formed 2D superlattices with hexagonal packing covering on the carbon-coated copper grids during the toluene evaporation. For all samples, the S 2p(3/2) and 2p(1/2) components that appeared at approximately 162 and approximately 163 eV, respectively, in the XPS spectra compare very well with the typical value of chemisorbed S species. Thermal analysis mass spectrometer was used to analyze desorption behavior of octanethiolated MPCs or pyridine-functionalized mixed MPCs. The TA-mass spectra have revealed that MCPs exist monomer and dimer desorption behavior from monomeric thiolate adsorbed on the surface.

Superlattice of octanethiol-protected copper nanoparticles.

The synthesis and spectroscopic characterizations of size-controlled Cu nanoparticles forming self-assembled 2D superlattices with hexagonal packing are described. The scanning electron microscopy (SEM), nuclear magnetic resonance (NMR), thermal gravimetric analysis (TGA), and electron spectroscopy for chemical analysis (ESCA) techniques were used to characterize the octanethiol-protected copper nanoparticles.

Synthesis and redox behavior of biferrocenyl-functionalized ruthenium(II) terpyridine gold clusters.

Spectroscopic and electrochemical characterizations of ferrocene- and biferrocene-functionalized terpyridine octanethiolate monolayer-protected clusters were investigated and reported. The electrochemical measurements of Ru2+ coordinated with 4'-ferrocenyl-2,2':6',2' '-terpyridine and 4'-biferrocenyl-2,2':6',2' '-terpyridine complexes were dominated by the Ru2+/Ru3+ redox couple (E(1/2) at approximately 1.3 V), Fe(2+)/Fe(3+) redox couples (E(1/2) from approximately 0.6 to approximately 0.9 V), and terpy/terpy-/terpy2- redox couples (E(1/)(2) at ca. -1.2 and ca. -1.4 V). The substantial appreciable variations detected in the Ru2+/Ru3+ and Fe2+/Fe3+ oxidation potentials indicate that there is an interaction between the Ru2+ and Fe2+ metal centers. The coordination of the Ru2+ metal center with 4'-ferrocenyl-2,2':6',2' '-terpyridine and 4'-biferrocenyl-2,2':6',2' '-terpyridine leads to an intense 1[(d(pi)Fe)6] --> 1[d(pi)Fe)5(pi*terpyRu)1] transition in the visible region. The 1[(d(pi)Fe)6] -->1[d(pi)Fe)5(pi*terpyRu)1] transition observed at approximately 510 nm revealed that there was a qualitative electronic coupling between metal centers. The coordination of the Ru2+ transition metal center lowers the energy of the pi*terpy orbitals, causing this transition.

Electroactive self-assembled biferrocenyl alkanethiol monolayers on Au(111) surface and on gold nanoclusters.

The spectroscopic and electrochemical characterizations of electrochemically stable biferrocene-modified Au clusters and chemisorbed biferrocenylalkanethiols on Au(111) surface were studied. The characterizations of biferrocene-modified Au cluster using TEM, UV-vis, and NMR techniques are also reported. Two successive reversible one-electron redox waves were observed for the biferrocenylalkanethiol Au nanoclusters and biferrocenylalkanethiol monolayers on Au(111) surface in the cyclic voltammetry. Furthermore, the positive and negative current peaks for each redox wave occur at almost the same potential, and the peak current increases almost linearly with the sweep rate. Repeat scanning does not change the voltammograms, demonstrating that these monolayers are stable to electrochemical cycling. The coverages of electroactive biferrocene in the monolayers were calculated from the cyclic voltammograms. The standard electron-transfer rate constant was calculated from the splitting between the oxidation and reduction peaks.