Kinetics and mechanism of the aminolysis of aryl N-ethyl thiocarbamates in acetonitrile

The aminolysis of aryl N-ethyl thiocarbamates (EtNHC(=O)SC(6)H(4)Z) with benzylamines (XC(6)H(4)CN(2)NH(2)) in acetonitrile at 30.0 degrees C is investigated. The rates are faster than the corresponding values for aryl N-phenyl thiocarbamates (PhNHC(=O)SC(6)H(4)Z), reflecting a stronger push to expel the leaving group by EtNH than the PhNH nonleaving group in a concerted process. The negative rho(XZ) (-0.86) and failure of the reactivity-selectivity principle found are consistent with the concerted mechanism. The kinetic isotope effects involving deuterated nucleophiles (k(H)/k(D) = 1.5-1.7) and low Delta H(++) with large negative Delta S(++) values suggest a hydrogen bond cyclic transition state.     

Fabric‐hydrogel composite membranes for culturing microalgae in semipermeable membrane‐based photobioreactors

In this article, we demonstrate that hydrogel‐based composite membranes are used as semipermeable materials for the construction of photobioreactors (PBRs). PBRs are developed to culture microalgae using nutrients dissolved in seawater, and thus they need to be fabricated with membranes possessing sufficient material‐transport properties. While hydrogels are characterized by their highly swelling nature in water and therefore have desirable transport of dissolved matter, they lack the mechanical strength to be cast into thin structures of large surface area. This issue motivated us to design a new concept, i.e., fabric‐hydrogel composite membranes ( FHCM s). A cotton fabric inside the hydrogel matrix endows the composite with tensile strength, which enables casting of FHCM s into thin membranes. Several FHCM s were prepared with 2‐hydroxyethyl methacrylate ( HEMA ), cross‐linking poly(ethylene glycol) dimethacrylate ( PEGDMA ) and a sheet of gauze by controlling the composition of the monomers and water. In the permeability measurement of nitrate ions, a key ingredient for the growth of microalgae, the permeability coefficient reached as high as 1.2 x 10^?8 m² min^?1, which is roughly three times higher than that of a commercially available semipermeable membrane (3.3 x 10^?9 m² min^?1). In the following evaluation of microalgal culture, a PBR constructed with a FHCM was able to maintain sufficient ion concentration and pH of the culture broth, supporting microalgal growth. These results suggest that the composite membranes with hydrogel and fabric have potential in the application of microalgal culture for bio‐diesel production in a marine environment. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 108–114     

Band alignment and defect states in amorphous GaInZnO thin films grown on SiO2/Si substrates

The band alignment and defect states of GaInZnO thin films grown on SiO₂/Si via radio frequency (RF) magnetron sputtering were investigated by using X‐ray photoelectron spectroscopy, reflection electron energy loss spectroscopy, thermally stimulated exo‐electron emission and photo‐induced current transient spectroscopy.The band gap via reflection electron energy loss spectroscopy was 3.2 eV. The defect states via photo‐induced current transient spectroscopy and thermally stimulated exo‐electron emission were at 0.24, 0.53, 1.69 and 2.01 eV below the conduction band minimum of GIZO thin films, respectively. The defect states at 0.24 and 0.53 eV are related to the field‐effect mobility, and the defect stated at 1.69 and 2.01 eV is related to the oxygen vacancy defect. Copyright © 2016 John Wiley & Sons, Ltd.     

Thermal and electro-optical properties of cerium-oxide-doped liquid-crystal devices

Doping with cerium (IV) oxide (CeO₂) nanoparticles can significantly enhance the thermal stability and electro-optical (EO) properties of nematic liquid crystal (NLC) systems. Thermal stability was improved without aggregation and reduction of transmittance by adding CeO₂ nanoparticles in a liquid crystal medium. In particular, the EO properties greatly improved in CeO₂-dispersed NLC cells. The threshold voltage reduced from 3.027 to 2.279 V and the response time decreased from 13.097 to 9.970 ms with increased CeO₂ nanoparticles in the NLC cells. The improved properties of liquid crystals doped with CeO₂ nanoparticles depend on the anchoring energy and the electric field of the CeO₂-dispersed liquid crystal displays.     

Hydrogel-shelled biodegradable microspheres for sustained release of encapsulants

Biodegradable microparticles are promising for the sustained release of encapsulated lipophilic drugs. In particular, the microparticles with uniform size show excellent linearity of cumulated release over time with minimized initial burst. Here, we encapsulate the biodegradable microparticles with a hydrogel shell to improve the controllability over the sustained release and suspension stability. With a capillary microfluidic device, monodisperse oil-in-water-in-oil (O/W/O) double-emulsion droplets are produced to have a toluene solution of polylactic acid (PLA) in the core and sodium alginate and calcium-ethylenediaminetetraacetic acid (EDTA) complex in the shell, whereas the continuous oil phase contains acetic acid. As the toluene evaporates, PLA consolidates to form a microsphere in the core. At the same time, acetic acid diffuses from the continuous phase to the water layer, which causes the dissociation of the Ca-EDTA complex and the gelation of alginate. The hydrogel-shelled PLA microspheres are transferred from the oil to an aqueous solution of calcium chloride, which further tightens the gel shell. The resulting core-shell microspheres show sustained release of encapsulants for extended periods as the hydrogel shell serves as a diffusion barrier. Moreover, the hydrogel shells prevent interparticle agglomeration and adhesion to the solid walls, securing high suspension stability during the injection.     

Magnetic field effect and controlling of Li amounts of cathode material for high performance in LIC

Journal of Solid State Electrochemistry - Li-doped high surface area of activated carbon (LHSAC) for Li ion capacitor (LIC) has been prepared by controlling the LiOH amounts for surface...     

Domino tilings of the expanded Aztec diamond

The expanded Aztec diamond is a generalized version of the Aztec diamond, with an arbitrary number of long columns and long rows in the middle. In this paper, we count the number of domino tilings of the expanded Aztec diamond. The exact number of domino tilings is given by recurrence relations of state matrices by virtue of the state matrix recursion algorithm, recently developed by the author to solve various two-dimensional regular lattice model enumeration problems.