Modeling and simulation of chemo-electro-mechanical behavior of pH-electric-sensitive hydrogel

A chemo-electro-mechanical multi-field model, termed the multi-effect-coupling pH-electric-stimuli (MECpHe) model, has been developed to simulate the response behavior of smart hydrogels subject to pH and electric voltage coupled stimuli when the hydrogels are immersed in a pH buffer solution subject to an externally applied electric field. The MECpHe model developed considers multiphysics effects and formulates the fixed charge density with the coupled buffer solution pH and electric voltage effects, expressed by a set of nonlinear partial differential governing equations. The model can be used to predict the hydrogel displacement and the distributive profiles of the concentrations of diffusive ionic species and the electric potential and the fixed charge density in both the hydrogels and surrounding solution. After validation of the model by comparison of current numerical results with experiment data extracted from the literature, one-dimensional steady-state simulations were carried out for equilibrium of the smart hydrogels subject to pH and electric coupled stimuli. The effects of several important physical conditions, including the externally applied electric voltage, on the distributions of the concentrations of diffusive ionic species, the electric potential, the fixed charge density, and the displacement of the hydrogel strip were studied in detail. The effects of the ionic strength on the bending deformation of the hydrogels under the solution pH and electric voltage coupled stimuli are also discussed.     

Solid-phase synthesis of pyrazolines and isoxazolines with sodium benzenesulfinate as a traceless linker

[reaction: see text] The preparation of pyrazoline and isoxazoline derivatives with traceless solid-phase sulfone linker strategy is described. Key steps involved in the solid-phase synthetic procedure include (i) sulfinate S-alkylation, (ii) sulfone anion alkylation, (iii) gamma-hydroxy sulfone --> gamma-ketosulfone oxidation, and (iv) traceless product release via elimination-cyclization. A library of 12 pyrazolines and isoxazolines was synthesized.     

Chemistry of condensed thiophenes. IV. Acetylation of phenanthro[4,5-bcd]thiophene

Treatment of phenanthro[4,5-bcd]thiophene ( 2 ) with acetyl chloride and aluminum chloride in nitrobenzene gives acetylation of positions ortho and para to the heteroatomic sulfur atom. In separate experiments, mixtures of 1- and 3-acetyl (50% yield, ratio 1.9:1) or of 1,5-, 1,7-, and 3,5-diacetyl (79% yield, ratio 3:1:1) derivatives were obtained. Isolated as isomerically pure products were the 1-acetyl and the 1,5-diacetyl compounds, as well as the oximes of the 1- and 3-acetyl derivatives. Comparison of these results is made with those reported for nitration of 2 , which also occurs ortho and para to the sulfur atom, and with nitration and acetylation of pyrene (the benzolog of 2 ) which substitutes in the corresponding positions.     

Nucleophilic substitution by arenethiolates at the carbene carbon of pentacarbonyl(methoxymethylcarbene)-metal(o) complexes (metal = Cr,Mo, or W)

The phenylthiocarbene complexes, [(CO)₅MC(CH₃)(SPh)] (M = Cr, Mo, or W) have been prepared in good yield by the reaction of [(CO)₅MC(CH₃)(OCH₃)] (M = Cr, Mo, or W) with NaSPh in benzene/methanol in the presence of HCl. A series of para-substituted phenylthiocarbene complexes of tungsten. [(CO)₅WC(CH₃)SC₆H₄Y)], (Y = p-Br, p-F, p-H, p-CH₃, p-OCH₃ or p-OH) have also been prepared by the reaction of the appropriate arenethiolate ion with [(CO)₅WC(CH₃)(OCH₃)]. Poor nucleophiles such as p-nitrobenzenethiolate and pentafluorobenzenethiolate did not react with [(CO)₅WC(CH₃)(OCH₃) to form the corresponding phenylthiocarbene complex. A mechanism accounting for the formation of these phenylthiocarbene complexes is proposed. The complexes have been characterized by their infrared, electronic, mass, ¹H NMR, and ¹³C NMR spectra. These spectroscopic data have been used to establish the structure of these complexes in solution and indicate that the phenyl ring bonded to sulfur is probably not coplanar with the “carbene” plane.     

Solid-phase synthesis of imidazo[1,2-a]pyridine using sodium benzenesulfinate as a traceless linker

[formula: see text] The preparation of the first library of imidazo[1,2-a]pyridine derivatives on a solid support is described. A sulfone linker strategy was applied in the synthesis. Key steps involved in the solid-phase synthetic procedure include (i) alpha-haloketone resin formation by sulfinate-->sulfone alkylation, (ii) imidazo[1,2-a]pyridine ring formation by treatment with 2-aminopyridine, (iii) sulfone anion alkylation, and (iv) traceless product release by oxidation-elimination. A library of 12 imidazo[1,2-a]pyridines was synthesized.     

Role of 2‐oxo and 2‐thioxo modifications on the proton affinity of histidine and fragmentation reactions of protonated histidine

A combination of electrospray ionisation (ESI), multistage and high‐resolution mass spectrometry experiments was used to compare the gas‐phase chemistry of the amino acids histidine (1), 2‐oxo‐histidine (2), and 2‐thioxo‐histidine (3). Collision‐induced dissociation (CID) of all three different proton‐bound heterodimers of these amino acids led to the relative gas‐phase proton affinity order of: histidine >2‐thioxo‐histidine >2‐oxo‐histidine. Density functional theory (DFT) calculations confirm this order, with the lower proton affinities of the oxidised histidine derivatives arising from their ability to adopt the more stable keto/thioketo tautomeric forms. All protonated amino acids predominately fragment via the combined loss of H₂O and CO to yield a₁ ions. Protonated 2 and 3 also undergo other small molecule losses including NH₃ and the imine HN=CHCO₂H. The observed differences in the fragmentation pathways are rationalised through DFT calculations, which reveal that while modification of histidine via the introduction of the oxygen atom in 2 or the sulfur atom in 3 does not affect the barriers against the loss of H₂O+CO, barriers against the losses of NH₃ and HN=CHCO₂H are lowered relative to protonated histidine. Copyright © 2010 John Wiley & Sons, Ltd.     

Triple negative permeability band in plasmon-hybridized cut-wire-pair metamaterials

We expand the picture of plasmon hybridization in metamagnetic structure via numerically studying the electromagnetic coupling in the metallic cut-wire-pair super cells. It is shown that a triple negative permeability band can be achieved by systematically controlling the plasmon hybridization in such the structure. The corresponding transmission properties as well as the electromagnetic responses of the plasmon-hybridized structures were presented by using the finite integration technique simulations. Our results would reveal a promising design to obtain the multiple negative refractions based on the combination of hybridized cut-wire-pairs and continuous wires.     

A microscopic pedestrian-simulation model and its application to intersecting flows

We develop a microscopic pedestrian-simulation model in which pedestrian positions are updated at discrete time steps. At each time step, each pedestrian probabilistically selects a direction of movement from a predetermined set according to a logit-type function that considers the dynamics of other pedestrians around, and then selects a step size that satisfies a certain distribution. We perform a number of field experiments on real intersecting pedestrian flows with four different angles. We then validate and calibrate the model using sample data on the deviation angles, step velocities, and velocity–density relations obtained from the experiments.     

Perfect impedance-matched left-handed behavior in combined metamaterial

Matching the impedance of a medium to free space, which is usually not available in natural materials, is an important advance in metamaterials. In this paper, we present a simple mechanism for a perfect impedance-matched left-handed metamaterials, that reveals a nearly zero reflection over operating frequency. This finding is based on the independent manipulation of the electric response without any effect on the magnetic one.