Ozone electrogeneration on Pt-TaO_y sol-gel film modified titanium electrode: Effect of electrode composition on the electrocatalytic activity

This work examines the ozone electrogeneration(OE) at a binary coating of different nominal compositions(Pt)x-(TaOy)(100-x), where x(percentage in the precursor solution) varied between 1% and 100%, coated on titanium substrate prepared by a sol-gel technique. TheOE is performed in an artificial tap water at room temperature(25C). The percentages of Pt and TaOy in the coating significantly affect the electrocatalytic activity towards oxygen evolution. The oxygen evolution was retarded to a different extent based on the electrode composition. The largest retardation was obtained at the(Pt)10-(TaOy)90 electrode(ca. 480 m V positive shift) as compared with the(Pt)100-(TaOy)0 electrode.This was reflected in a high current efficiency(CE) ofOE(ca. 19.3%) at the former electrode. This value is considered to be among the highest values reported forOE at 25C in neutral media. The composite electrodes were characterized by voltammetric and surface techniques. A plausible explanation for the change of the efficiency ofOE with the electrode composition is given based on the electrochemical results.     

Preparation of cellulosic soft and composite materials using ionic liquid media and ion gels

Cellulose - Ionic liquids (ILs) are powerful media for the modification and functionalization of cellulose. This review article discusses the preparation of cellulosic soft and composite materials...     

Phosphorescent Ruthenium Complexes with a Nitroimidazole Unit that Image Oxygen Fluctuation in Tumor Tissue

Understanding oxygen fluctuation in a cancerous tumor is important for effective treatment, especially during radiotherapy. In this paper, ruthenium complexes bearing a nitroimidazole group are shown to report the oxygen status in tumor tissue directly. The nitroimidazole group was known to be accumulated in hypoxic tumor tissues. On the other hand, the ruthenium complex showed strong phosphorescence around 600 nm. The emission of ruthenium is quenched instantaneously by molecular oxygen due to energy transfer between triplet states of oxygen and ruthenium complex, but the emission is then recovered by the removal of oxygen. Thus, we could observe oxygen fluctuation in tumor tissue in a real‐time manner by monitoring the phosphorescence of the ruthenium complex. The versatility of the probe is demonstrated by monitoring oxygen fluctuation in living cells and tumor tissue planted in mice. The ruthenium complex promptly penetrated plasma membrane and accumulated in cells to emit its oxygen‐dependent phosphorescence. In vivo experiments revealed that the oxygen level in tumor tissue seems to fluctuate at the sub‐minute timescale.     

Total Synthesis of (−)‐Isoschizogamine

The total synthesis of (?)‐isoschizogamine was accomplished, featuring the construction of the quaternary carbon center by the modified Johnson–Claisen rearrangement in basic media and the facile assembly of the key tetracyclic quinolone intermediate through a cascade cyclization. The characteristic cyclic aminal was constructed by late‐stage C?H functionalization at the position adjacent to the lactam nitrogen using a combination of CrO₃ and nBu₄NIO₄ and subsequent Bi(OTf)₃‐mediated cyclization.     

Hydrogen Peroxide Formation by Electric Discharge with Fine Bubbles

Pulsed discharge plasma is typical oxidation technology for disposing organic compounds in aqueous solutions. When this electrical discharge plasma was applied in water, it may produce hydrogen peroxide (H₂O₂) without any catalyst or chemical agent. In order to increase H₂O₂ production by electrical discharge plasma in water, fine bubbles were introduced into the electrical discharge plasma in this experiment. Bipolar pulsed voltages were applied to cylindrical electrodes in the water while Ar or O₂ bubbles were introduced, generating a pulsed discharge plasma. The introduction of the bubbles seemed to enhance the dissociation of water molecules and increased H₂O₂ formation, especially with O₂ bubbling. Dissolved oxygen in the water contributed to H₂O₂ formation by pulsed discharge plasma with the bubbles, while dissociation of water molecules was the cause of H₂O₂ formation by pulsed discharge plasma without bubbles. More H₂O₂ was formed by pulsed discharge plasma with O₂ bubbles, because the amount of dissolved oxygen in the water increased upon bubbling with O₂.     

The elastic-plastic stress distribution near the flat surfaced notch with cycloidal tip in a work-hardening material

Summary Based on a deformation theory of plasticity, the stress distribution near an edge crack having finite root radius in strain-hardening material is given for the case of antiplane shear (Mode III). The approximate solution is derived in an analytical form by using Neuber's result and integral J by Rice.

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Übersicht Unter Zugrundelegung der Deformationstheorie der Plastizität wird die Spannungsverteilung in der Nähe eines Randrisses mit endlichem Radius für den Fall des nichtebenen Schubspannungszustandes (Mode III) und eines dehnungsverfestigenden Materials gegeben. Die angenäherte Lösung wird durch Verwendung der Ergebnisse von Neuber sowie dem J-Integral von Rice in analytischer Form erhalten.

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In honour of the 70th birthday of Professor H. Neuber.     

New Preparation of Cyclic Acyloxyphosphorane by Reaction of Glyoxylic Acid with Phosphorus(III) Compounds

We have recently found that the reaction of α-keto acids (1) with phosphorus (III) compounds (3) yielded cyclic acyloxyphosphoranes(C-AOPs, 4), a new class of pentacovalent phosphorus species having a P-OC(O) group.^{1, 2)} The present paper deals with a new reaction of glyoxylic acid (2) with 3 to give C-AOPs (5) having no substituent at the C-3 position. 1 is an α-keto acid whereas 2 can be taken as an α-formyl acid. Although it is well known in the field of organic chemistry that the formyl group often behaves differently from a keto group, the reaction of 2 with 3 provides an example in which both groups behave in a similar manner.     

Nonclassical Urea Oligomers. VII. Binding Specificity of Carbanilido-ethylenimine Oligomer: Absorption Behavior in Suspension

Polyester elastomers were prepared by block copolymerization of dimethyl terephthalate (DMT), butanediol (BDO), and polytetramethylene glycol (PTMG). Polyester from DMT and butanediol forms a high-melting hard segment in block copolyester to prevent undue chain slippage when fibers are stretched. High elongation was provided by soft segment which consisted of condensation product from DMT and PTMG.

Experiments were carried out to determine the effect of composition variables on the properties of these elastomers, such as glass transition temperature, elongation at break, tenacity, and elastic recovery. The study on molecular characteristics of the elastic polyester showed that a leather-like region exists between glassy and rubbery regions. These elastomers were melt-spun to give elastic fibers which are competitive with commercially available Spandex-type fibers.     

Polymerization of Cyclic Ethers

Abstract

In the present series of studies on the cationic polymerization of cyclic ethers, the reactivities of cyclic ethers were quantified and the effect of the catalyst upon the polymerization kinetics was revealed. These kinetic analyses were successfully performed by means of our “phenoxyl end-capping method”. The change of the reactivity by the ring size of the monomer was interestingly demonstrated. In addition, it is emphasized that the frequency factor as well as the activation energy influence the rate constant of propagation. As to the effect of catalyst upon the polymerization kinetics, the most important conclusion is that the rate constant of propagation changes very little according to the changes of the catalyst components. Variation of the conversion rate by a change of catalyst is due to differences in the rates of the initiation and the termination reactions.     

Synthesis and Polymerization of Spiro Oxyphosphoranes

Novel methods of synthesis of spiro acyloxyphosphoranes are described emphasizing the significance of the first isolated instance of these new species. Then, the no-catalyst alternating copolymerizations of the combinations of cyclic phosphorus(III) compounds (serving as nucleophilic monomer, M_N) with acrylic acid derivatives and with α-keto acids (electrophilic monomer, M_E) are mentioned. These copolymerizations proceed without added initiator. Spiro oxyphosphoranes play an important role in the copolymerization scheme in the equilibrium with the ⁺M_N - M_E ^? zwitterion, the key intermediate of the copolymerization. Finally, new reactions of spiro acyloxyphosphoranes with nucleophiles, alcoholysis and aminolysis polymerizations are presented.