Weak disorder: anomalous transport and diffusion are normal yet again

We carry out a detailed study of the motion of particles driven by a constant external force over a landscape consisting of a periodic potential corrugated by a small amount of spatial disorder. We observe anomalous behavior in the form of subdiffusion and superdiffusion and even subtransport over very long time scales. Recent studies of transport over slightly random landscapes have focused only on parameters leading to normal behavior, and while enhanced diffusion has been identified when the external force approaches the critical value associated with the transition from locked to running solutions, the regime of anomalous behavior had not been recognized. We provide a qualitative explanation for the origin of these anomalies, and make connections with a continuous time random walk approach.     

Synthesis and aggregation of cationic porphyrins

Tetra(N-R-pyridinium-4-yl)porphyrin and tetra(N-R-pyridinium-3-yl)porphyrin derivatives were synthesized with R = 3, 6, and 8 carbon alkene, alcohol and carboxylic acid chains. Self-aggregation of these systems was studied at I = 0.1 using visible spectroscopy. N-Alkyl chain length and functionality were determined to play the dominant role in aggregation of the cationic porphyrins. Position of peripheral charge (meta vs. para) also influenced spectral changes and the nature of the aggregate.     

Fabrication of high quality silicon–polyaniline heterojunctions

A high quality silicon–polyaniline heterojunction is produced by spin-coating of soluble polyaniline on silicon substrates. The devices have excellent reproducibility of their electrical characteristics and high rectification ratio. The rectification ratio is 60,000 at ±1.0 V at room temperature, and typical reverse current at −1.0 V is 3 nA. A G/I×G plot is used to analyze the current–voltage characteristics, yielding typical series resistance of 4 kΩ and ideality factor in a range from 1.0 to 2.0. The devices present great potential for use as radiation and/or gas sensors.     

Androgynous porphyrins. Silver(II) quinoxalinoporphyrins act as both good electron donors and acceptors

The metal-centered and macrocycle-centered electron-transfer oxidations and reductions of silver(II) porphyrins were characterized in nonaqueous media by electrochemistry, UV-vis spectroelectrochemistry, EPR spectroscopy, and DFT calculations. The investigated compounds are {5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)porphyrinato}silver(II), {5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)quinoxalino[2,3-b']porphyrinato}silver(II), {5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)bisquinoxalino[2,3-b':7,8-b']porphyrinato}silver(II), and {5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)bisquinoxalino[2,3-b':12,13-b']porphyrinato}silver(II). The first one-electron oxidation and first one-electron reduction both occur at the metal center to produce stable compounds with Ag(III) or Ag(I) metal oxidation states, irrespective of the type of porphyrin ligand. The electrochemical HOMO-LUMO gap, determined by the difference in the first oxidation and first reduction potentials, decreases by introduction of quinoxaline groups fused to the Ag(II) porphyrin macrocycle. This provides a unique androgynous character to Ag(II) quinoxalinoporphyrins that enables them to act as both good electron donors and good electron acceptors, something not previously observed in other metalloporphyrin complexes. The second one-electron oxidation and second one-electron reduction of the compounds both occur at the porphyrin macrocycle to produce Ag(III) porphyrin pi-radical cations and Ag(I) porphyrin pi-radical anions, respectively. The macrocycle-centered oxidation potentials of each quinoxalinoporphyrin are shifted in a negative direction, while the macrocycle-centered reduction potentials are shifted in a positive direction as compared to the same electrode reactions of the porphyrin without the fused quinoxaline ring(s). Both potential shifts are due to a stabilization of the radical cations and radical anions by pi-extension of the porphyrin macrocycle after fusion of one or two quinoxaline moieties at the beta-pyrrolic positions of the macrocycle. Introduction of quinoxaline groups fused to the Ag(II) porphyrin macrocycle provides a unique androgynous character to Ag(II) quinoxalinoporphyrins that enables them to act as both good electron donors and good electron acceptors.     

A facile synthesis of aliphatic thiol surfactant with tunable length as a stabilizer of gold nanoparticles in organic solvents

Three new aliphatic thiol surfactants were synthesized by reacting alkyl bromide with hexamethyldisilathiane under a mild condition. This approach provides an easy access for the direct synthesis of various different length thiol surfactants which play a crucial role in tuning the properties of gold nanoparticles. Gold nanoparticles encapsulated with one of our synthetic thiols were prepared and well characterized by H NMR, UV-vis, FT-IR, and TEM. The hybrid nanoparticles are very stable in both organic solvents and the solid state.     

Aspect ratio effects in turbulent duct flows studied through direct numerical simulation

Three-dimensional effects in turbulent duct flows, i.e., sidewall boundary layers and secondary motions, are studied by means of direct numerical simulation (DNS). The spectral element code Nek5000 is used to compute turbulent duct flows with aspect ratios 1–7 (at Re_{b, c} = 2800, Re_{τ, c} ? 180) and aspect ratio 1 (at Re_{b, c} = 5600, Re_{τ, c} ? 330), in streamwise-periodic boxes of length 25h. The total number of grid points ranges from 28 to 145 million, and the pressure gradient is adjusted iteratively in order to keep the same bulk Reynolds number in the centreplane with changing aspect ratio. Turbulence is initiated via a trip forcing active during the initial stages of the simulation, and the statistical convergence of the data is discussed both in terms of transient approach and averaging period. Spanwise variations in wall shear, mean-flow profiles, and turbulence statistics are analysed as a function of aspect ratio, and also compared with the spanwise-periodic channel (as idealisation of an infinite aspect ratio duct). The computations show good agreement with experimental measurements carried out in parallel at the Illinois Institute of Technology (IIT) in Chicago, and highlight the relevance of sidewall boundary layers and secondary vortices in the physics of the duct flow. The rich array of secondary vortices extending throughout the upper and lower walls of the duct, and their dependence on Reynolds number and aspect ratio, had not been reported in the literature before.     

Rapid Synthesis of Porous Honeycomb Cu/Pd through a Hydrogen‐Bubble Templating Method

A rapid electrochemical method based on using a clean hydrogen‐bubble template to form a bimetallic porous honeycomb Cu/Pd structure has been investigated. The addition of palladium salt to a copper‐plating bath under conditions of vigorous hydrogen evolution was found to influence the pore size and bulk concentration of copper and palladium in the honeycomb bimetallic structure. The surface was characterised by X‐ray photoelectron spectroscopy, which revealed that the surface of honeycomb Cu/Pd was found to be rich with a Cu/Pd alloy. The inclusion of palladium in the bimetallic structure not only influenced the pore size, but also modified the dendritic nature of the internal wall structure of the parent copper material into small nanometre‐sized crystallites. The chemical composition of the bimetallic structure and substantial morphology changes were found to significantly influence the surface‐enhanced Raman spectroscopic response for immobilised rhodamine B and the hydrogen‐evolution reaction. The ability to create free‐standing films of this honeycomb material may also have many advantages in the areas of gas‐ and liquid‐phase heterogeneous catalysis.     

Spectral characterization and intracellular detection of Surface‐Enhanced Raman Scattering (SERS)‐encoded plasmonic gold nanostars

Plasmonic gold nanostars offer a new platform for surface‐enhanced Raman scattering (SERS). However, due to the presence of organic surfactant on the nanoparticles, SERS characterization and application of nanostar ensembles in solution have been challenging. Here, we applied our newly developed surfactant‐free nanostars for SERS characterization and application. The SERS enhancement factors (EF) of silver spheres, gold spheres and nanostars of similar sizes and concentration were compared. Under 785 nm excitation, nanostars and silver spheres have similar EF, and both are much stronger than gold spheres. Having plasmon matching the incident energy and multiple ‘hot spots’ on the branches bring forth strong SERS response without the need to aggregate. Intracellular detection of silica‐coated SERS‐encoded nanostars was also demonstrated in breast cancer cells. The non‐aggregated field enhancement makes the gold nanostar ensemble a promising agent for SERS bioapplications. Copyright © 2012 John Wiley & Sons, Ltd.     

Sensitive voltammetric determination of xanthinol nicotinate at a carbon nanotubes-ionic liquid gel modified electrode

The electrochemistry of xanthinol nicotinate(Xan) was studied by cyclic voltammetry at a glassy carbon electrode modified by a gel containing multi-walled carbon nanotubes(MWNTs) and room-temperature ionic liquid of 1-butyl-3-methylimidazolium hexafluorophosphate(BMTMPF_6).The modified electrode exhibited good promotion to the electrochemical oxidation of Xan and an ultrasensitive electrochemical method was proposed for the determination of Xan.This method was successfully applied to the determination of...