Electrodiffusion Model Simulation of Ionic Channels: 1D Simulations

The drift-diffusion (Poisson-Nernst-Planck) model is applied to ionic channels in biological membranes plus surrounding solution baths. Simulations of the K channel in KCl solutions using the TRBDF2 method are presented which show significant boundary layers at the ends of the channel. The computed current-voltage curve for the K channel shows excellent agreement with experimental measurements.     

GC-MS detected difunctional carboxylic acids released by driedCladophora at the pH of lake ontario and the st. lawrence river

A study to identify the acidic components ofCladophora glomeata active againstAedes triseriatus larvae was extended to a mixture obtained by extracting the dried powdered alga in aqueous suspension at pH 8.5. The presence of 1,9-nonanedioic, 1,10-decanedioic, 1,11-undecanedioic and 4-ketononanoic acids was determined by GC-EIMS and GC-CIMS and confirmed by analytical coinjection GC. The presence of 5-pentyldihydro-2(3H)-furanone, a minor component, was also indicated. The group of major acidic constituents is different from those obtained by extracting driedCladophora with methanol. In contrast to the C₁₀–C₁₄ monocarboxylic acids, which hadLD ₅₀ values<20 ppm againstA. triseriatus, none of the dicarboxylic acids of the series G₄–C₁₄, C₁₆, and C₂₂ were active; nor were 4-ketononanoic acid and 5-pentyldihydro-2(3H)-furanone active.     

Polyamide 6–Cellulose Composites: Effect of Cellulose Composition on Melt Rheology and Crystallization Behavior

Melt rheology and crystallization behavior of polyamide 6 (PA 6) and microcrystalline cellulose (MCC) composites were systematically studied in this research. The incorporation of MCC into the PA 6 matrix resulted in higher complex viscosities (|η*|), storage modulus (G′), and shear viscosities than those of neat PA 6, especially at low frequencies. The orientation of rigid molecular chains in the composites introduced by the addition of MCC induced a strong shear thinning behavior with an increase in MCC loading. The non‐isothermal crystallization kinetics of PA 6 and MCC composites were investigated by differential scanning calorimetry. The Avrami and Tobin model were applied to describe the process of non‐isothermal crystallization and to determine the crystallization parameters of the composites. Analysis of the crystallization kinetics indicated that the Avrami (n_a) and Tobin exponent (n_t) was altered by the MCC. It was also found that the Avrami and Tobin equations fit the empirical data well. POLYM. ENG. SCI., 54:739–746, 2014. © 2013 Society of Plastics Engineers     

Synthesis,structure, and characterization of the thorium zirconolite CaZr1-xThxTi2O7 system

A series of zirconolite ceramics with composition CaZr_1-xTh_xTi₂O₇ (Δx = 0.10) were reactively sintered at 1350°C for 20 h, in air (0 ≤ x ≤ 0.60) and 5% H₂/N₂ (0 ≤ x ≤ 0.40). A sample with composition corresponding to x = 0.20 was also produced by hot isostatic pressing (HIP) at 1300°C and 100 MPa for 4 hours. Th⁴⁺ immobilization was most readily achieved under oxidizing conditions, with Th⁴⁺ preferentially incorporated within a pyrochlore-structured phase in the range 0.10 ≤ x ≤ 0.50, yet formation of the zirconolite-4M polytype was not observed. We report the novel synthesis of single-phase pyrochlore with nominal composition CaZr_0.40Th_0.60Ti₂O₇ when targeting x = 0.60. Th⁴⁺ incorporation under reducing conditions produced a secondary Th-bearing perovskite, comprising 24.2 ± 0.6 wt% of the phase assemblage when targeting x = 0.40, alongside 8.8 ± 0.3 wt% undigested ThO₂. Under reducing conditions, powder XRD data were consistent with zirconolite adopting the 3T polytype structure. The sample produced by HIP presented a nonequilibrium phase assemblage, yielding a major phase of zirconolite-2M alongside accessory Th⁴⁺-bearing phases ThTi₂O₆, ThO₂, and perovskite. These data highlight the efficacy of Th⁴⁺ as a Pu⁴⁺ surrogate, with implications for the formation of Zr-stabilized Th-pyrochlore phases as matrices for waste with elevated Th⁴⁺ content.     

Influence of melt stability on the crystallization of bis(4-aminophenoxy)benzene-oxydiphthalic anhydride based polyimides

Novel high performance semicrystalline polyimides, based on controlled molecular weight phthalic anhydride (PA) endcapped 1,4-bis(4-aminophenoxy)benzene (TPEQ diamine) and oxydiphthalic dianhydride (ODPA), were synthesized. They exhibited excellent thermal stability in nitrogen and air atmospheres as determined by thermogravimetric analysis (TGA). The glass transition temperatures (T_g) for these polymers ranged from 225°C for the 10,000 M_n (10K) polymer, to 238°C for the 30,000 (30K) M_n material. The observed melting temperatures for all the polymers were ∼420°C. The crystallization behavior of these polymers showed a strong molecular weight dependence, as illustrated by the observation that the 10K and 12.5K polymers crystallized with relative ease, whereas the 15K, 20K, and 30K polymers showed little or no ability to undergo thermal recrystallization. The thermal stability of these polymers above T_m was investigated by studying the effect of time and temperature in the melt on the cold crystallization and melting of these polymers. Increased time and temperature in the melt resulted in lower crystallinity because of melt state degradation, such as crosslinking and branching, as evidenced by an increase in melt viscosity, which was more prominent for the higher molecular weight polymers.     

Synthesis and Antiangiogenic Properties of Tetrafluorophthalimido and Tetrafluorobenzamido Barbituric Acids

The development of novel thalidomide derivatives as immunomodulatory and anti‐angiogenic agents has revived over the last two decades. Herein we report the design and synthesis of three chemotypes of barbituric acids derived from the thalidomide structure: phthalimido‐, tetrafluorophthalimido‐, and tetrafluorobenzamidobarbituric acids. The latter were obtained by a new tandem reaction, including a ring opening and a decarboxylation of the fluorine‐activated phthalamic acid intermediates. Thirty compounds of the three chemotypes were evaluated for their anti‐angiogenic properties in an ex vivo assay by measuring the decrease in microvessel outgrowth in rat aortic ring explants. Tetrafluorination of the phthalimide moiety in tetrafluorophthalimidobarbituric acids was essential, as all of the nonfluorinated counterparts lost anti‐angiogenic activity. An opening of the five‐membered ring and the accompanying increased conformational freedom, in case of the corresponding tetrafluorobenzamidobarbituric acids, was well tolerated. Their activity was retained, although their molecular structures differ in torsional flexibility and possible hydrogen‐bond networking, as revealed by comparative X‐ray crystallographic analyses.     

Wallace E. Lambert (1922–2009).

On August 23, 2009, psychology lost an innovative researcher with the passing, at 86, of Wallace E. Lambert. A professor of psychology at McGill University from 1954 until 1990, Wallace (“Wally”) Lambert was among the founders of psycholinguistics and sociolinguistics. His highly productive career included contributions to social and cross-cultural psychology (intergroup attitudes, child-rearing values, and psychological consequences of living in multicultural societies), language education (the French immersion program), and bilingualism (measurement of language dominance, attitudes and motivation in second-language learning, and social, cognitive, and neuropsychological consequences of bilingualism). Indeed, because of the scope and influence of his work, Wally Lambert is widely considered the father of the psychological study of bilingualism. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Partial oxidation of methane over Rh/supported-ceria catalysts: Effect of catalyst reducibility and redox cycles

Partial oxidation of methane (POM) was studied over Rh/(Ce_0.56Zr_0.44)O_2−x, Rh/(Ce_0.91Gd_0.09)O_2−x, Rh/(Ce_0.71Gd_0.29)O_2−x and Rh/(Ce_0.88La_0.12)O_2−x. The effect of catalyst reducibility and redox cycles was investigated. It was found that the type of doped-ceria support and its reducibility played an important role in catalyst activity. It was also observed that redox cycles had a positive influence on H₂ production, which was enhanced as the number of redox cycle increased. Results of carbon formation are discussed as a function of ionic conductivity. Temperature programmed reduction (TPR) profiles, BET surface area, ionic conductivity and XRD patterns were determined to characterize catalysts. Catalytic tests revealed that of the materials tested, Rh/(Ce_0.56Zr_0.44)O_2−x was the most active material for the production of syngas, which correlates with its TPR profile. It was observed that doping CeO₂ with Zr, rather than with La or Gd caused an enhanced reducibility of Rh/supported-ceria catalysts.     

A calorimetric examination of coal surfaces

This communication reports the results of some exploratory experiments to examine the surface of coal by (i) flow microcalorimetry (FM) and (ii) vapour sorption calorimetry (VSC). Excepting differential scanning calorimetry, calorimetric methods have not been widely-exploited in coal structure research. The intent of this short communication is to demonstrate that hitherto neglected calorimetric methods are very rewarding when applied to the study of coal surfaces.