Electrochemical insertion and extraction of lithium-ion at nano-sized LiMn2O4 particles prepared by a spray pyrolysis method

Nano-sized LiMn₂O₄ particles were prepared at 1023 K by electrospray pyrolysis in which they were directly deposited on a Pt substrate in gas phase. Cyclic voltammetry gave very sharp and symmetrical redox peaks at ca. 4.0 and 4.1 V vs. Li/Li⁺ owing to the insertion and extraction of lithium-ion at LiMn₂O₄. However, the redox peaks broadened and their peak separation in an electrode potential increased when aggregated nano-sized LiMn₂O₄ particles were used. In Nyquist plots, a semi-circle due to lithium-ion transfer resistance appeared at potentials above 3.90 V. The values of the lithium-ion transfer resistances were small for dispersed nano-sized LiMn₂O₄ particles. On the other hand, the lithium-ion transfer resistances increased and the Warburg impedance became obvious as the nano-sized LiMn₂O₄ particles aggregated. These results clearly indicate that the apparent rapid diffusion of lithium-ion can be attained using well-dispersed nano-sized particles of electroactive materials.     

Removal of proteins from natural rubber with urea and its application to continuous processes

The removal of proteins from natural rubber through a batch process was studied by the incubation of the rubber latex with urea in the presence of sodium dodecyl sulfate. Under suitable conditions, the total nitrogen content of deproteinized natural rubber (DPNR) decreased from 0.38 to 0.02 wt % after incubation for 10 min; this was similar to that of the rubber deproteinized with a proteolytic enzyme for 12 h. For applications, continuous incubation and centrifugation were individually investigated by the use of a semicircular channel and a continuous centrifuge, respectively, to scale up DPNR preparation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of satellite bubbles on dynamics of gas absorption from a CO2 bubble into a downward-flowing liquid

The dynamic process of gas absorption from a CO₂ bubble into a liquid is examined in the presence of satellite bubbles. The bubble under consideration is held stationary, except its jittering, by the liquid flowing downward. The mass transfer rate is determined by monitoring the rate of reduction in the equivalent bubble diameter during the initial absorption process. It is found that the interaction with the satellite bubbles generally hampers the dissolution of the primary bubble. The extent of reduction in the dissolution rate increases with the net contacting time during the interaction. When the secondary bubbles interact with the primary bubble mainly outside of its wake, however, the dissolution tends to be enhanced due to induced turbulence in the surrounding liquid flow. A simple theoretical model is developed to simulate the observed results as well as the basic features prevailing in a recently proposed scheme, called the GLAD system, for shallow injection of CO₂ gas into seawater.     

Phase Transformation of Hydrous-Zirconia Fine Particles Containing Cerium Hydroxide

Monoclinic hydrous-zirconia fine particles that contained cerium(IV) hydroxide (Ce(OH)₄) were heated from 200°C to 600°C, to investigate the phase transformation to CeO₂-doped tetragonal ZrO₂. Both ZrOCl₂·8H₂O and CeCl₃·7H₂O were dissolved in aqueous solutions and then boiled to prepare the hydrous-zirconia particles. The Ce(OH)₄-containing hydrous-zirconia particles were prepared by adding aqueous ammonia into the boiled solutions. The monoclinic-to-tetragonal ( m right arrow t ) phase transformation of the Ce(OH)₄-containing hydrous zirconias was observed at 300°C using X-ray diffraction (XRD). XRD and Brunauer-Emmett-Teller (BET) specific surface area measurements revealed that the Ce(OH)₄-containing hydrous zirconias had a tendency to transform from the monoclinic phase to the tetragonal phase at lower temperatures as the primary particle size of the hydrous zirconia decreased and the Ce(OH)₄ content increased. These tendencies for the m right arrow t phase transformation agree with the conclusions that have been derived from thermodynamic and kinetic considerations.     

Electrochemical reduction of carbon dioxide to ethylene with high Faradaic efficiency at a Cu electrode in CsOH/methanol

The electrochemical reduction of CO₂ with a Cu electrode in CsOH/methanol-based electrolyte was investigated. The main products from CO₂ were methane, ethylene, ethane, carbon monoxide and formic acid. A maximum Faradaic efficiency of ethylene was 32.3% at −3.5 V vs. Ag/AgCl saturated KCl. The best methane formation efficiency was 8.3% at −4.0 V. The ethylene/methane current efficiency ratio was in the range 2.9–7.9. In the CsOH/methanol, the efficiency of hydrogen formation, being a competitive reaction against CO₂ reduction, was depressed to below 23%.     

Phase-transformation and grain-growth kinetics in yttria-stabilized tetragonal zirconia polycrystal doped with a small amount of alumina

Microstructure development during sintering in 3 mol% Y₂O₃-stabilized tetragonal zirconia polycrystal doped with a small amount of Al₂O₃ was investigated in the isothermal sintering conditions of 1300–1500 °C. At the low sintering temperature at 1300 °C, although the density was relatively high, the grain-growth rate was much slow. In the specimen sintered at 1300 °C for 50 h, Y³⁺ and Al³⁺ ions segregated along grain boundaries within the widths of about 10 and 6 nm, respectively. In grain interiors, the cubic-phase regions were formed by not only a grain-boundary segregation-induced phase-transformation mechanism but also by spinodal decomposition. The grain-growth behavior was kinetically analyzed using the grain-size data in 1300–1500 °C, which indicated that the grain-growth rate was enhanced by Al₂O₃-doping. These phase-transformation and grain-growth behaviors are reasonably explained by the diffusion-enhanced effect of Al₂O₃-doping.     

Quantitative analysis for reaction between epoxidized natural rubber and poly (L‐lactide) through 1H‐NMR spectroscopy

Reaction between epoxidized natural rubber and poly(L ‐lactide) (PLLA) was investigated quantitatively in terms of conversion of the epoxidized natural rubber. The epoxidized natural rubber was prepared by epoxidation of high ammonia natural rubber (HA‐NR) or deproteinized natural rubber (DPNR) with peracetic acid followed by depolymerization with ammonium persulfate. The resulting liquid HA‐NR having epoxy group (LENR) or liquid DPNR having epoxy group (LEDPNR) were subjected to heating at 473 K for 20 min, after blending with PLLA. The products were characterized through morphology observation, DSC measurement, and ¹H‐NMR spectroscopy. The conversions of the rubbers were estimated from intensity ratio of signals in ¹H‐NMR spectrum for the products after removing unreacted rubber with toluene. Difference in the estimated conversion between the LENR/PLLA and LEDPNR/PLLA blends was interpreted in relation to proteins present in the rubber. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Porphylipoprotein Accumulation and Porphylipoprotein Photodynamic Therapy Effects Involving Cancer Cell-Specific Cytotoxicity

In photodynamic therapy (PDT) for neoplasms, photosensitizers selectively accumulate in cancer tissue. Upon excitation with light of an optimal wavelength, the photosensitizer and surrounding molecules generate reactive oxygen species, resulting in cancer cell-specific cytotoxicity. Porphylipoprotein (PLP) has a porphyrin-based nanostructure. The porphyrin moiety of PLP is quenched because of its structure. When PLP is disrupted, the stacked porphyrins are separated into single molecules and act as photosensitizers. Unless PLP is disrupted, there is no photosensitive disorder in normal tissues. PLP can attenuate the photosensitive disorder compared with other photosensitizers and is ideal for use as a photosensitizer. However, the efficacy of PLP has not yet been evaluated. In this study, the mechanism of cancer cell-specific accumulation of PLP and its cytotoxic effect on cholangiocarcinoma cells were evaluated. The effects were investigated on normal and cancer-like mutant cells. The cytotoxicity effect of PLP PDT in cancer cells was significantly stronger than in normal cells. In addition, reactive oxygen species regulated intracellular PLP accumulation. The cytotoxic effects were also investigated using a cholangiocarcinoma cell line. The cytotoxicity of PLP PDT was significantly higher than that of laserphyrin-based PDT, a conventional type of PDT. PLP PDT could also inhibit tumor growth in vivo.