Syndiotactic‐specific radical polymerization of N‐isopropylacrylamide in toluene at low temperatures in the presence of silyl alcohols

The radical polymerization of N‐isopropylacrylamide was carried out in toluene at low temperatures in the presence of silyl alcohols, such as triethylsilanol. Poly(N‐isopropylacrylamide) with a racemo dyad content of 75% was obtained at ? 80 °C with a 4:1 triethylsilanol to monomer ratio loading. NMR analysis suggests that the mechanism for syndiotactic induction, in the presence of silyl alcohols, may be similar to that observed with alkyl alcohols. In this case, a 1:2 complex formation, via hydrogen bonding interactions, leads to the induction of syndiotactic specificity. Copyright © 2012 Society of Chemical Industry     

Simulation of a chemical reaction, 2LiH→Li2+H2, driven by doubly excitation

A direct computer simulation of reaction dynamics at the electronic excited states is not easy to perform, because nonadiabatic equations must be solved as a function of time. Here we present a simple simulation to integrate directly the time-dependent Schrödinger equation within the framework of the time-dependent density functional theory (for electrons) coupled with the Newtonian equation of motion (for nuclei). We find that a chemical reaction, 2LiH→Li₂+H₂, takes place by the doubly excitation. Along the reaction, a level crossing occurs automatically between the highest occupied and lowest unoccupied levels. The simulation demonstrates a mechanism for relaxation for the reactions driven by doubly excitation: electronic excited state changes smoothly into the electronic ground state leaving a kinetic energy of the atoms.     

WO3/BiVO4 composite photoelectrode prepared by improved auto-combustion method for highly efficient water splitting

We report on the improvement in the water splitting efficiency of a WO₃/BiVO₄ composite photoelectrode by the application of an improved auto-combustion method to the preparation of porous BiVO₄ thin films. The unique feature of this preparation method is the addition of both NH₄NO₃, as a strong oxidizing agent, and an organic additive into BiVO₄ precursor solution. The local decomposition heat of the organic additive and oxidizing agent created a porous film with small, highly crystalline BiVO₄ particles. The photoelectrode has many advantages over existing ones, such as the high light-harvesting efficiency (LHE), a single BiVO₄ phase, the facile access of the holes to the photoelectrode/electrolyte interface, and the ease of water and oxygen diffusion. The maximum incident photon-to-current efficiency (IPCE) was estimated to be 64% (at 440 nm, 1.23 V vs. RHE) and the applied bias photon-tocurrent efficiency (ABPE) reached as high as 1.28%. This ABPE value is highest among all oxide semiconductor photoelectrodes reported previously, except for the case of a stacking photoelectrode system.     

Ozonation of N-Nitrosamines in the Reverse Osmosis Concentrate from Water Recycling Applications

This study aims to evaluate the performance of ozone treatment for removing N-nitrosamines from reverse osmosis (RO) concentrate in water recycling applications. In the absence of any N-nitrosamine precursors, the destruction efficiency of N-nitrosamines was dependent on their molecular weight or the length of the alkyl chain in their molecular structure. Experiments conducted with RO concentrate showed that ozonation could lead to the formation of N-nitrosodimethylamine (NDMA) and N-nitrosodiethylamine (NDEA), resulting in an increase in concentrations of these N-nitrosamines. Nevertheless, ozonation was effective for destruction of N-nitrosamines with molecular weight greater than that of NDEA (102 g/mol).     

Development of Sensor and Control Systems of a Wearable Robot to Walk on a Step

The goal of our study is to develop a system for walking on a step using a wearable robot. Our system consists of (1) sensing of a step from the movement of the walker, (2) detection of the foot placement state related to the step, and (3) generation of gait patterns of climbing and stepping down for the step. In the generation of gait patterns for the step, toe trajectories are generated according to the height of the step to avoid collision of the swinging leg with the step. The hip trajectory is generated by an optimization technique that minimizes the sum of the joint angular jerk of the robot subject to constraints on the hip position and the velocity at toe liftoff. Each joint angle trajectory is calculated from the generated trajectories by means of inverse kinematic equations. We investigated the feasibility of the proposed sensor and control systems for two steps with different heights.     

Cloning and characterization of a β-N-acetylglucosaminidase (BmFDL) from silkworm Bombyx mori

In insects, β-N-acetylglucosaminidase (GlcNAcase) participates in critical physiological processes such as fertilization, metamorphosis, and glycoconjugate degradation. Insects produce glycoproteins carrying paucimannosidic-type N-glycans, the terminal GlcNAc residue of which is cleaved by a GlcNAc-linkage specific GlcNAcase, also known as the fused lobes (FDL) protein. To obtain information on the structure of GlcNAcases and insight into their contribution to physiological processes, we cloned Bombyx mori FDL (BmFDL) from silkworm larvae. The full-length cDNA (1.9 kb) encoded a protein of 633 amino acids with 42% amino acid sequence identity to Drosophila melanogaster FDL (DmFDL). Recombinant BmFDL cleaved only β-1,2-linked GlcNAc residues from the α-1,3 branch of biantennary N-glycan. This substrate specificity was similar to that of DmFDL. Microsomal FDL activity was inhibited by anti-BmFDL antibodies. Taken together, our results suggest that BmFDL is a N-glycan-processing GlcNAcase in B. mori.     

Synthesis of zirconia sphere particles based on gelation of sodium alginate

Zirconia sphere particles were synthesized through the gelation process of Na-alginate, and cermet (ZrO₂-Mo) pellets were fabricated under several conditions. In this process, a zirconia slurry was prepared by mixing oxide powders (ZrO₂, Y₂O₃, Er₂O₃, CeO₂), distilled water and Na-alginate, and subsequently dropped into CaCl₂ solution. As a result, zirconia sphere particles coated with a gelled film were synthesized. The slurry density (zirconia content in slurry) of 30-64 wt.% and Na-alginate concentration of a few% were good for gelation for up to 10 wt.% CaCl₂ solution. Sphere particles with smaller diameter were obtained by dropping slurry with a mechanical vibration. The prolongation of the ball milling time for mixture of oxide powders was effective to increase the sintered density of zirconia sphere particles, especially for higher CeO₂ concentration. The dense cermet pellets were fabricated for max. 50% volume ratio of zirconia phase for Mo matrix using zirconia particles covered with Mo powder by a rotating granulation method.     

Soft-type polyurethane foams derived from molasses

Molasses (ML)-based soft-type polyurethane (PU) foams were successfully prepared by controlling evolved heat during chemical reaction. Two kinds of isocyanate, poly(phenylene methylene) polyisocyanate (MDI) and tolylene diisocyanate (TDI), and polypropylene glycol with a long molecular chain length were utilized to control the chemical reaction. The hydroxyl group in ML was used as the reaction site and soft-type PU foams were synthesized at isocyanate (NCO)/hydroxyl group (OH) ratios of 1.05. Mechanical properties of the above foams were controlled by changing the mixing ratio of MDI and TDI. Pore size and distribution were measured by scanning electron microscopy. With increasing thickness of cell wall, compression strength and modulus increased. Thermal properties of PU foams were investigated by differential scanning calorimetry, thermogravimetry, and thermal conductivity measurements. Two-step glass transition temperatures were observed at around ca. ?55 and 80 °C, regardless of kind of isocyanate. The low temperature side glass transition is attributed to the molecular motion of long oxyethylene chains and the high temperature side transition is caused by rigid components including saccharide components. Thermal decomposition of PU foams started from ca. 270 °C. Thermal conductivity of soft-type PU was observed in a range from 0.034 to 0.035 J s^?1 m^?1 K^?1.