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)     

High mobility p-channel organic field effect transistors on flexible substrates using a polymer-small molecule blend

Organic field effect transistors have been fabricated on poly(ethylene terephthalate) film substrates with excellent operating characteristics and maximum mobilities of 1.1 cm²/(V s). The semiconductor was a solution processible blend of 6,13-bis(triisopropyl silylethynyl) pentacene and a poly(triaryl amine) used to combine the favourable properties of small molecules and polymers. We have demonstrated that such systems are a good candidate for flexible organic electronics and that the surface energy of the substrate plays a key role in controlling the morphology of the semiconductor film.     

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.     

Biosynthesis of galactomannan in the endosperms of developing fenugreek (Trigonella foenum-graecum L.) and guar (Cyamopsis tetragonoloba [L.] Taub.) seeds

The biosynthesis of galactomannan in vitro has been demonstrated conclusively using particulate enzyme preparations from the developing endosperms of fenugreek and guar and the sugar nucleotides GDP-D-mannose and UDP-D-galactose. Furthermore the mannose: galactose (man:gal) ratio in the products formed in vitro has been manipulated. These results are discussed in the context of possible mechanisms for the control of man:gal ratio in vivo.     

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.     

Asphyxial death caused by a laryngeal schwannoma: a case report

Neurogenic tumours of the larynx are unusual, with approximately 115 cases reported in the literature to date. Most of these lesions are benign, solitary submucosal nodules which present with hoarseness and are amenable to surgical resection. We present a case of a large pedunculated schwannoma arising in the aryepiglottic fold associated with sudden asphyxial death in an otherwise healthy young female.     

Children's deliberateness of planning according to task circumstances.

89 children ages 4 to 9 solved mazes varying in the presumed appropriateness of advance or improvisational planning. Using a between-Ss design, children's performance was compared in a standard condition that stressed accuracy in problem solving (designed to increase the importance of advance planning to avoid errors) and a variation stressing speed (designed to favor improvisational planning). Performance was compared by varying maze structure in terms of whether errors in route choices could be identified from a search of a small portion of the maze (favoring improvisation) or from a search through the entire maze (favoring advance planning). Children's planning strategies were stable over trials and had predictable effects on error rates. Children's usage of deliberate planning strategies was related to the circumstances of the problem, with more advanced planning when the structure of the mazes and instructions favored that strategy. Children used less advance planning when speed was a consideration and when the maze structure allowed avoidance of errors without extensive search. Results show that children's planning strategies are adapted to circumstances, and suggest that older children may be more proficient in this adaptation than are younger children. (PsycINFO Database Record (c) 2010 APA, all rights reserved)