Dithienylethene-Based Single Molecular Photothermal Linear Actuator

By employing a mechanically controllable break junction technique, we have realized an ideal single molecular linear actuator based on dithienylethene (DTE) based molecular architecture, which undergoes reversible photothermal isomerization when subjected to UV irradiation under ambient conditions. As a result, open form (compressed, UV OFF) and closed form (elongated, UV ON) of dithienylethene-based molecular junctions are achieved. Interestingly, the mechanical actuation is achieved without changing the conductance of the molecular junction around the Fermi level over several cycles, which is an essential property required for an ideal single molecular actuator. Our study demonstrates a unique example of achieving a perfect balance between tunneling width and barrier height change upon photothermal isomerization, resulting in no change in conductance but a change in the molecular length, which results in mechanical actuation at the single molecular level.     

Fluorescence emission of disperse Red 1 in solution at room temperature

In this article, we report the fluorescence emission of Disperse Red 1 in solution at room temperature and pumping at 532 nm with a 25 mW diode laser. We have measured its fluorescence quantum yield in methanol, ethylene glycol, glycerol, and phenol obtaining values as high as 10(-3) in the aliphatic alcohols. The excitation spectra of Disperse Red 1 in all four solvents as well as its excitation anisotropy in glycerol are presented. Applying a Gaussian decomposition method to the absorption spectra along with the support from the excitation spectra, the positions of the different transitions in this pseudo-stilbene azobenzene dye were determined. Solvatochromic and isomerization constraint effects are discussed. Calculations using density functional theory at TD-B3LYP/6-31G*//HF/6-31G* level were performed to interpret the experimental observations.     

On the stabilization of conducting pernigraniline salt by the synthesis and oxidation of polyaniline in hydrophobic ionic liquids

The electrochemical polymerization of aniline in a hydrophobic room-temperature ionic liquid and the spectroelectrochemical characterization of the formed film are presented. The polymerization occurs without the presence of acid in 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide (BMMITFSI), leading to a very stable electroactive material where no degradation was observed even at high applied potentials. Both in situ UV-Vis and Raman spectroscopic studies provided evidence for the stabilization of pernigraniline salt at high oxidation potentials and that this polyaniline state is the conducting form, as was corroborated by in situ resistance measurements. These data are indicative that low conductivity is not an intrinsic property of pernigraniline salt and this point must be reconsidered.     

Kinetics of the Anionic Polymerization of Buta‐1,3‐diene Considering Different Reactivities of the cis,trans and vinyl Structural Units

The anionic solution polymerization of buta‐1,3‐diene was modeled, considering the reactivity of the active sites to be different due to varying geometric configurations. With the first‐order Markov model, expressions for the fraction of active sites and dyad distribution were obtained. The rate constants were determined by fitting to the conversion and dyad experimental data using the nonlinear least squares method. The kinetic model shows that the microstructure and the dyads do not depend on initiator and butadiene concentration but only on rate constants. Without a modifier, the butadiene addition mechanism is entropic; with a modifier, the mechanism changes to entropic‐enthalpic.

     

Electron-phonon interaction in magnesium: From the monolayer to the Mg(0 0 0 1) surface

We report ab initio study of the electron-phonon coupling in a free standing magnesium monolayer and at the Mg(0 0 0 1) surface. The calculations were carried out using a linear-response approach in the plane-wave pseudopotential representation. Eliashberg spectral function α²F(ω) averaged over electron states at the Fermi surface is presented for the monolayer while for the Mg(0 0 0 1) surface, we compute the electron-phonon spectral function α²F_k,i(ω) for surface states at the and points.     

Electron-phonon contribution to hole linewidth of the surface state on Al(0 0 1)

We report an ab initio study of the electron-phonon interaction and its contribution to the excited hole linewidth of the surface state on Al(0 0 1). We have also evaluated the phonon-induced contribution to the linewidth of the occupied energy bands of Δ₁ symmetry in bulk Al. The calculations were carried out using a linear response approach in the plane-wave pseudopotential representation.     

Rheology and contact lifetimes in dense granular flows

We study the rheology and distribution of interparticle contact lifetimes for gravity-driven, dense granular flows of noncohesive particles down an inclined plane using large-scale, three dimensional, granular dynamics simulations. Rather than observing a large number of long-lived contacts as might be expected for dense flows, brief binary collisions predominate. In the hard-particle limit, the rheology conforms to Bagnold scaling, where the shear stress is quadratic in the strain rate. As the particles are made softer, however, we find significant deviations from Bagnold rheology; the material flows more like a viscous fluid. We attribute this change in the collective rheology of the material to subtle changes in the contact lifetime distribution involving the increasing lifetime and number of the long-lived contacts in the softer particle systems.     

Aza-Nazarov reaction and the role of superelectrophiles

The superacid-catalyzed reactions of N-acyliminium ion salts have been studied. The new conversions are remarkably similar to the Nazarov reaction and dicationic superelectrophilic species are thought to be involved. Experimental studies show that the cyclizations may be used to prepare varied heterocyclic products, while theoretical studies show that formation of the superelectrophiles can lead to very favorable reaction energetics.     

Determination of lead in wine by hydride generation atomic fluorescence spectrometry in the presence of hexacyanoferrate(III)

A rapid, accurate, and precise method is described for the determination of Pb in wine using continuous-flow hydride generation atomic fluorescence spectrometry (CF-HGAFS). Sample pretreatment consists of ten-fold dilution of wine followed by direct plumbane generation in the presence of 0.1 mol L⁻¹ HCl and 1% m/v K₃[Fe(CN)₆] with 1% m/v NaBH₄ as reducing agent. An aqueous standard calibration curve is recommended for Pb quantification in wine sample. The method provides a limit of detection and a limit of quantification of 0.3 μg L⁻¹ and 1 μg L⁻¹, respectively. The relative standard deviation varies between 2–6% (within-run) and 4–11% (between-run) at 3–30 μg L⁻¹ Pb levels in wine. Good agreement has been demonstrated between results obtained by CF-HGAFS and direct electrothermal atomic absorption spectrometry in analyses of red and white wines within the concentration range of 9.2–25.8 μg L⁻¹ Pb.