Chemically modified proton‐conducting membranes based on sulfonated polyimides: Improved water stability and fuel‐cell performance

A series of branched/crosslinked sulfonated polyimide (B/C‐SPI) membranes were prepared and evaluated as proton‐conducting ionomers based on the new concept of in situ crosslinking from sulfonated polyimide (SPI) oligomers and triamine monomers. Chemical branching and crosslinking in SPI oligomers with 1,3,5‐tris(4‐aminophenoxy)benzene as a crosslinker gave the polymer membranes very good water stability and mechanical properties under an accelerated aging treatment in water at 130 °C, despite their high ion‐exchange capacity (2.2–2.6 mequiv g^?1). The resulting polymer electrolytes displayed high proton conductivities of 0.2–0.3 S cm^?1 at 120 °C in water and reasonably high conductivities of 0.02–0.03 S cm^?1 at 50% relative humidity. In a single H₂/O₂ fuel‐cell system at 90 °C, they exhibited high fuel‐cell performances comparable to those of Nafion 112. The B/C‐SPI membranes also displayed good performances in a direct methanol fuel cell with methanol concentrations as high as 50 wt % that were superior to those of Nafion 112. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3751–3762, 2006     

OXIDATION-REDUCTION REACTIONS OF P700 AND CYTOCHROME f IN FRACTION 1 PARTICLES PREPARED FROM SPINACH CHLOROPLASTS BY FRENCH PRESS TREATMENT

Abstract— –Fraction-1 particles were prepared by passing spinach chloroplasts three times through the French pressure cell and centrifuging in a sucrose gradient. With the electron donor DAD (diaminodurol or 2,3,5,6-tetramethyl-p-phenylenediamine) and ascorbate, a light-induced difference spectrum revealed the oxidation of both cytochrome f and P700 upon illumination of these particles. The oxidation of cytochrome f was completed in less than 0.5 msec. P700 and cytochrome f thus seem to be tightly bound to each other in these particles. Addition of Triton X-100 abolished the fast oxidation of cytochrome f but not that of P700. Artificial electron donors such as DAD, DCIP (2,6-dichlorophenol indophenol), and PMS (N-methylphenazonium methosulfate) were good electron donors for photoreaction 1 in these particles, while neither plastocyanin, Porphyra cytochrome 553, nor Euglena cytochrome-552 reduced P700 efficiently. However, after treatment of fraction 1 particles with Triton X-100 reduced DAD, DCIP and PMS were no longer efficient electron donors, while plastocyanin and the algal cytochromes were highly active in reducing P700. Mammalian cytochrome c was not a good electron donor either before or after Triton treatment. Measurements of the effectiveness of P700 reduction as a function of concentration in Triton-treated particles showed plastocyanin to be about four times more active than Porphyra or Euglena cytochromes which in turn were about fourteen times more active than mammalian cytochrome c. Recent studies by Murata and Brown have shown that plastocyanin is not required for the reduction of NADP in these particles with DCIP and isoascorbate as electron donors. The present investigation and that of Murata and Brown indicate that disintegration of chloroplasts with the French pressure cell and centrifugation in a sucrose gradient is the best method to separate system-1 particles having an electron-transport system in almost the native state as in chloroplasts.     

Controlled assembly of silica microspheres in spherically confined polymer particles by using self-organized precipitation (SORP) method

Assembly of submicron-sized microspheres has received much attention due to its high potential for wide variety of applications. We have developed a preparation method of polymer particles by simple mixing of a poor solvent into the polymer solution followed by evaporation of a good solvent. By using this technique, silica nanoparticles and polymer composite particles were prepared. Preparation of three-dimensional assemblies of silica particles in polymer particles and composite Janus particles are shown.     

Equivalent cross-relaxation rate imaging positively correlates with pathological grade and cell density of adipocytic tumors

Objective

Equivalent cross-relaxation rate imaging (ECRI) is an MRI technique used to evaluate qualitative changes in protein-water interactions. We aimed to prospectively evaluate the utility of ECRI for classification of adipocytic tumors.

Materials and Methods

Institutional Review Board approval was obtained and all patients provided informed consent. Study participants included 40 patients with adipocytic tumors who were diagnosed with lipomas (n = 22), atypical lipomatous tissue/well-differentiated liposarcoma (ALT/WDL; n = 9), myxoid/round cell liposarcoma (MyL; n = 6), and dedifferentiated liposarcoma (DDL; n = 3), and 20 control patients for whom subcutaneous fat in the buttock or thigh was analyzed.

Results

Mean ECR values of lipomas, ALT/WDL, and subcutaneous fat were low, and those of MyL and DDL were high. Mean ECR values of MyL and DDL were significantly higher than those of ALT/WDL. The cut-off value was 5.1%. There was a positive correlation between ECR value, pathological grade, and cell density in adipocytic tumors.

Conclusion

The ECR value positively correlates with pathological grade and cell density of adipocytic tumors. Our findings suggest that ECRI is a useful method for preoperative evaluation of adipocytic tumors.     

Second-harmonic generation in thermally poled chalcohalide glass

Second-harmonic generation in 60GeS(2)-20Ga(2)S(3)-20KBr chalcohalide glass was investigated by the thermal poling method. A large second-order nonlinear susceptibility, as high as 7.0 pm/V, was obtained in a poled sample by Maker fringe analysis. We believe this to be the first time that a clear second-harmonic wave was observed in chalcohalide glasses containing large amount of alkali ions (6.25 at. %). Such observation is of great potential use in all optical waveguide devices.     

Proton conductivity and microstructures of the core-shell type solid electrolytes in the MO2-In2O3-P2O5 (MTi,Sn, Zr) systems

The proton conducting 0.9MO₂·0.05In₂O₃·1.3P₂O₅ (MTi, Sn, Zr) electrolytes based on a core-shell structure were synthesized by a ball milling method. The core-shell type electrolytes showed the proton conductivities ranging from a higher value than those of Nafion membranes to 10^? 5 Scm^? 1 at intermediate temperatures of 150–200 °C, depending on the heat-treatment conditions. The samples with high conductivity were proved to adopt a core-shell structure by SEM observation, powder XRD analysis and ³¹P MAS-NMR measurements.     

Syntheses and Mesomorphic Properties of New Liquid Crystalline Materials Involving Piperazine Skeleton

Some mesogenic materials involving a piperazine skeleton were prepared and the thermal properties were examined by DSC and microscopic analyses. Although the piperazines have a thermal flexibility similar to cyclohexyl ring, a lateral interaction due to lone pair electrons of nitrogens largely enhances the thermal stability of the mesophase. The piperazine compounds tend to preserve a smectic arrangement.