Ab initio modelling of basal plane oxidation of graphenes and implications for modelling char combustion

Ab initio calculations have been performed to determine the energetics of oxygen atoms adsorbed onto graphene planes and the possible reaction path extracting carbon atoms in the form of carbon monoxide. From the energetics it is confirmed that this reaction path will not significantly contribute to the gasification of well ordered carbonaceous chars. Modelling results which explore this limit are presented.     

Potential use of chemical cues for colony-mate recognition in the big brown bat,Eptesicus fuscus

Bats should benefit from recognition of their roost-mates when colonies form stable social units that persist over time. We used Y-maze experiments and gas chromatography–olfactometry (GC-O) to evaluate whether female big brown bats Eptesicus fuscus (Chiroptera: Vespertilionidae) use chemical cues to distinguish among conspecifics. In dual-choice Y-maze experiments, females chose the scent of another female from their own roost over a conspecific female from a different roost in a majority of trials. Analysis of total body odors using GC-O suggests that individuals from a given colony may share a more common odor signature with roost-mates than with non-roost-mate conspecifics. Using four principle components derived from 15 odor variables, discriminant function analysis correctly assigned most individuals to the correct colony.     

Comparison of the modelled thyroxine binding site in TBG with the experimentally determined site in transthyretin

The structure of cleaved thyroxine-binding globulin (TBG) hasbeen modelled on the crystal structure of cleaved 1-antitrypsin(a member of the serine proteinase inhibitor, serpin, superfamily)based on the high sequence homology exhibited by the two proteins.Particular attention was paid to the identification and modelledcharacteristics of the thyroxine binding site. The primary aimof the study was to compare the site qualitatively with thecrystallographically determined binding site of transthyretin,the other major transporter of thyroxine, in an attempt to explainthe higher binding affinity of the site compared with the knownthyrox ine binding site in transthyretin (10¹⁰ versus 10⁸ M^–1).The proposed binding site shares some similar characteristicswith the transthyretin binding site but also includes a clusterof aromatic residues which are entirely absent in transthyretin.It is proposed that this might account for the substantial differencein binding affinities.     

Lattice Constants of Boron Carbides

The lattice constants of boron carbides have been determined by powder X-ray diffraction for samples with compositions between about 7.7 and 20.5 at.% carbon. The boundaries of the single-phase region are at about 9 at.% carbon and near, but likely somewhat less than, 20 at.% carbon. The composition dependence of the lattice constants thus established provides a method of assessing the carbon concentration of unknown materials. In particular, assignment of the approximate composition of single crystals used in previous studies allows for a systematic examination of changes in interatomic separation as a function of composition. These changes are discussed in terms of a structural model of the boron carbide solid solution.     

Alumina Grown during Deposition of Thermal Barrier Coatings on NiCrAlY

The microstructure of Al₂O₃ formed by oxidation of a model NiCrAlY alloy during electron-beam physical vapor deposition of ZrO₂–7.6 mol% YO_1.5 is examined and compared with that formed on the bare substrate. The growth rate, morphology, and chemical composition of the oxide vary among the different constituents of the alloy surface and are further influenced by the O₂ partial pressure and the physical presence of the thermal barrier coating (TBC) layer. These differences, however, are largely limited to the outer oxide layer. The interplay between the TBC and the growing oxide leads to the formation of a fine-grain Al₂O₃–ZrO₂"mixed zone" within the thermally grown oxide. A mechanism is outlined to explain this behavior, based on the dissolution of ZrO₂ in a transient Al₂O₃ structure growing by outward diffusion of Al, and its subsequent reprecipitation when the metastable phase transforms to the stable α-Al₂O₃ form.     

Crystallization of hydroxybutyrate oligomers: 1. morphology and folding

Exact length hydroxybutyrate oligomers containing 24 and 32 repeat units have been prepared and their crystallization behaviour and crystal morphology observed.The oligomers form crystals from dilute solution and from the melt that have similar overall morphologies to crystals of the polymer, poly(hydroxybutyrate). Electron diffraction indicates that the chains are closely perpendicular to the basal planes of the crystals.Wide angle X-ray diffraction suggests that all crystals, no matter what their thickness, have a high degree of crystallinity and the same crystal structure.The crystals have a range of thicknesses, as measured by small angle X-ray diffraction. The most common thicknesses correspond to the extended stem length and to one half or, surprisingly, two thirds of that value. A model is proposed for the non-integer fraction crystals in which half of the chain ends are incorporated in the crystals themselves.     

Synthesis and physical properties of cuphea-oleic estolides and esters

Cuphea-oleic estolides and esters were synthesized from cuphea and oleic FA with various amounts of perchloric acid (0.01 to 0.40 equiv) at 60°C. Estolide yields ranged from 30 to 65% after Kugelrohr distillation. Estolide number (EN), the average number of FA units added to a base FA, varied with reaction conditions. Cuphea-oleic estolides were esterified with 2-ethylhexanol to obtain high yields of the corresponding ester. A streamlined, one-pot process was used to synthesize the estolide and its ester with 0.05 equiv of HClO₄, with, esterification incorporated into an in situ second step to provide a functional fluid at a very reasonable cost. The physical properties of the cuphea-oleic estolides and estolide esters, including their viscosities, pour points, and cloud points, were related directly to the amount of oligomerization (EN), i.e., viscosity increased with higher oligomerization. The viscosity index ranged from 132 to 166 cSt for the free-acid estolides, whereas the complex estolide 2-ethylhexyl esters had slightly high viscosity indices that ranged from 165 to 181 cSt. These new cuphea-oleic estolide esters displayed good low-temperature properties (pour point −42°C and cloud point −41°C).     

Application of Hyphenated Chromatography–Mass Spectrometry Techniques to Plant Allelopathy Research

Plant allelopathy offers hope as an additional means of weed control in modern agriculture. Its mechanisms and molecular basis are not yet well understood. Research on the chemical basis for allelopathy has often been hindered by the complexity of plant and soil matrices, making it difficult to track active compounds. Recent improvements in the cost and capabilities of bench-top chromatography–mass spectrometry instruments make these tools more powerful and more widely available to assist with molecular studies conducted in today's expanding field. Such instrumental techniques are herein recommended as economically efficient means of advancing the rigor of allelopathy research and assisting the development of a better understanding of the chemical basis for the allelopathy phenomenon.     

A highly regioselective synthesis of δ-lactones from meadowfoam fatty acids

Meadowfoam fatty acids, when treated with mineral acid catalysts in the presence of polar nonparticipating solvents, undergo a facile ring closure to form δ-lactones. Perchloric and sulfuric acids catalyze the cyclization at concentrations of 0.6–13 mole equivalents, both neat and in the presence of solvent. Under constant acid concentrations, methylene chloride was found to increase the rate of reaction, the regioselectivity for the formation of δ-lactone, and the overall yield. In the absence of solvent, increased acid concentration improved the yield of lactone but reduced regioselectivity for the δ-isomer. Solvent polarity plays a significant role in the regioselectivity of the cyclization for δ-lactone, with solvents of higher dielectric strength providing larger δ/γ ratios (38:1) and higher yields up to 92%.     

Flexible Backbone Aromatic Polyimide Adhesives

Continuing research at Langley Research Center on the synthesis and development of new inexpensive flexible aromatic polyimides as adhesives has resulted in a material identified as LARC-F-SO₂ with similarities to polyimidesulfone (PISO₂) and other flexible backbone polyimides recently reported by Progar and St. Clair. Also prepared and evaluated was an endcapped version of PISO₂. These two polymers were compared with LARC-TPI and LARC-STPI, polyimides researched in our laboratory and reported in the literature.

The adhesive evaluation, primarily based on lap shear strength (LSS) tests, involved preparing adhesive tapes, conducting bonding studies and exposing lap shear specimens to 204°C air for up to 1000 hrs and to a 72-hour water boil. LSS tests at RT, 177°C and 204°C were performed before (controls) and after these exposures. The type of adhesive failure as well as the Tg was determined for the fractured specimens.

The results indicate that LARC-TPI provides the highest LSSs, 33 MPa at RT, 30 MPa at 177°C, and 26 MPa at 204°C. LARC-F-SO₂, LARC-TPI and LARC-STPI all retain their strengths after thermal exposure for 1000 hrs and PISO₂ retains greater than 80% of its control strengths.

Most of the four adhesive systems showed reduced strengths for all test temperatures although they still retained a high percentage of their original strength (<60%) except for one case.

The predominant failure mode was cohesive with no significant change in the Tgs.

Although the LARC-F-SO₂ could not be prepared in diglyme alone as the solvent, the properties of the resulting adhesive were notable. The darkening of the adhesive during bonding was typical of systems which utilize amide solvents.