Pheromone biosynthesis in lepidoptera

Pheromone components for many lepidopteran species are produced by the use of unique chain-shortening and 9, 10, and 11 desaturase systems. Correlations in the Tortricidae indicate that the pheromone components derived from 9 and 01 desaturases are found in the more primitive species (those possessing morphological plesiomorphies). The precise blend ofZ andE acetates in a number of species is regulated in the final reduction sequence from acyl intermediates. Preliminary research has been conducted on the characterization of the various desaturase enzymes used and on the important blend regulating sequence. Initial purification work on the 11 desaturase enzyme found in the cabbage looper moth is reported.     

The manufacture of high-value carbon from coal-tar pitch

World-wide, 17 million ta^?1 of coal-tar are obtained as a by product in the chamber coking process for the production of metallurgical coke. Refining of this aromatic raw material yields coal-tar pitch which is the traditional coal-derived starting material for the manufacture of carbon precursors and carbon artefacts. Considerable progress has been made in the elucidation of the physical and chemical nature of this material by means of chromatography, n.m.r. spectroscopy, thermal analysis and chemical reactions schemes. The dominant fields of application of pitch are the manufacture of pitch coke and electrode binders. Delayed coking and horizontal chamber coking are the technologies currently used for the production of cokes with low sulphur and metal content, for anodes for the aluminium-refining industry and the electric steel process. Coal-tar pitch, low in quinoline-insolubles (QI), is an excellent raw material for the manufacture of needle-cokes with a low coefficient of thermal expension (CTE). The separation of inherent QI can be performed via gravity settling in aliphatic hydrocarbon mixtures, by centrifugation in a disc separator or by filtration. The possible co-carbonization with aromatic petroleum-derived residues yields premium coke suitable for the manufacture of UHP-electrodes. New developments in the production of coke from coal-tar pitch aim to improve coke yields and increase anisotropy (i.e. low CTE and high electrical conductivity values). Further technological progress has been made in the manufacture of hard pitch which can be used as a starting material for the production of pitch coke in the chamber coking process and for the production of electrode binders by means of a continuous flash process with optimized thermal and pressure treatment of pitch, thus facilitating the ‘tailored’ manufacture of binder pitches of different qualities.     

Random Copolymers with 2,2′-Dioxy-1,1′-biphenyl-phosphazene and Chiral 2,2′-dioxy-1,1′-binaphthylphosphazene Units Functionalized in the 6,6′-Positions with PPh<Subscript>2</Subscript> Groups as Precursors for Ru(arene) Catalysts

The chiral phosphazene copolymers {[NP(O₂C₁₂H₈)]_0.9[NP(O₂C₂₀H₁₂)]_0.1} (1) and {[NP(O₂C₁₂H₈)]_0.9[NP(O₂C₂₀H₁₀Br₂)]_0.1} _n (2) [(O₂C₁₂H₈) = 2,2′-dioxy-1,1′-biphenyl; (O₂C₂₀H₁₂) = R-2,2′-dioxy-1,1′-binaphthyl and (O₂C₂₀H₁₀Br₂) = R-6,6′-dibromo-2,2′-dioxy-1,1′-binaphthyl] were prepared by sequential substitution from [NPCl₂] _n and the corresponding dihydroxy-biphenyl or binaphthyl reagents in the presence of Cs₂CO₃ and K₂CO₃. The reaction of (2) with ^tBuLi in THF, followed by addition of PPh₂Cl and a treatment with SiHCl₃/PPh₃ to eliminate any oxidized OC₆H₄P(O)Ph₂ groups, gave the phosphine containing copolymer {[NP(O₂C₁₂H₈)]_0.9[NP(O₂C₂₀H₁₀[PPh₂]₂)]_0.1} _n (3), that was used as a chiral ligand to support [Ru(p-cymene)Cl] complexes. The resulting catalyst was active for hydrogen transfer from isopropyl alcohol to acetophenone but the placement of the Ru centers in the 6,6′-positions of the binaphthoxyphosphazene units induced no enantioselectivity. Dedicated to Professor Christopher Allen.     

Restructuring butterfat through blending and chemical interesterification. 3. Rheology

Interesterified and noninteresterified butterfat-canola oil blends, ranging from 100% butterfat to 60∶40 butterfat-canola oil (w/w) in 10% increments, were evaluated for hardness index (HI), dropping point, viscosity, and viscoelastic properties at small deformation. Both blending and chemical interesterification diminished HI in a nonlinear fashion. HI changes in interesterified blends were more pronounced than in noninteresterified blends. Dropping points yielded information on the structure of the blends. Butterfat’s dropping point (DP) was 34.4°C, whereas that of interesterified butterfat was 37.0°C, which is indicative of a more structured network for the latter. DP values of blends with 60–90% butterfat (interesterified vs. noninteresterified) were not significantly different (P<0.05). Interesterified blends had a higher crystallization onset temperature than did noninteresterified blends. All blends in the liquid state displayed Newtonian behavior. Oscillatory frequency sweep measurements at small amplitude showed that interesterified blends generally had lower storage moduli (G′) than their noninteresterified counterparts. BothG′ andG″ were frequency-dependent. Replacement of 30% butterfat by canola oil led to notable changes in small deformation measurements, whereas replacement of 20% butterfat led to big changes in large deformation measurements.     

<Emphasis Type="Italic">In situ</Emphasis> monitoring of solid fat content by means of pulsed nuclear magnetic resonance spectrometry and ultrasonics

An ultrasonic technique was developed to study the crystallization process of edible fats on-line. A chirp wave was used instead of the conventional pulser signal, thus achieving a higher signal-to-noise ratio. This enabled measurements to be made in concentrated systems [≈20% solid fat content (SFC)] through a 8.11-cm thick sample without significant signal loss. Fat samples were crystallized at 20, 25, and 30°C at a constant agitation rate of 400 rpm for 90 min. The crystallization process was followed by ultrasonic spectroscopy and a low-resolution pulsed nuclear magnetic resonance spectrometer. Specific relationships were found between ultrasonic parameters [integrated response, time of flight (TF), and full width half maximum] and SFC. TF, which is an indirect measurement of the ultrasonic velocity (v), was highly correlated to SFC (r ²>0.9) in a linear fashion (v=2.601 SFC+1433.0).     

Polyurethane‐infiltrated carbon foams: A coupling of thermal and mechanical properties

The thermal and mechanical properties of polyurethane‐infiltrated carbon foam of various densities were investigated. By combining the high thermal conductivity of the carbon foam with the mechanical toughness of the pure polyurethane, a mechanically tough composite (relative to the unfilled foam) that could be used at higher temperatures than the polyurethane's degradation was formed. Both the tensile strength and the modulus increased by an order of magnitude for the composites compared to unfilled foam, while the compressive and shear strengths and moduli of the composites approached values exhibited by pure polyurethane. At both 300 and 400°C, the rectangular blocks of pure polyurethane lost their mechanical integrity due to decomposition in air. Thermogravimetric analysis confirms substantial initial weight loss above 290°C. Filled carbon foam blocks, however, maintain their mechanical integrity at both 300 and 400°C indefinitely, although the bulk of the rectangular block mass is polyurethane. Three different carbon foam densities are examined. As expected, the higher density foams show greater heat transfer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2348–2355, 2003     

Thermal analysis of styrene–alkyl methacrylate polymers. I. Glass transition temperatures

The glass transition temperatures (T_g's) of several polystyrenes and styrene–alkyl methacrylate copolymers and terpolymers were measured using thermomechanical analysis (TMA) and differential scanning calorimetry (DSC). The polymers studied had number-average molecular weights from 3000 to 250,000 g/mole. The results indicate that the composition dependence of the T_g's for the copolymers and terpolymers can be satisfactorily described by a general Fox equation. In general, the measured T_g's of the copolymer and terpolymer samples depend more on the steric effects of the constituent pendent groups than on their molecular weights. The chain flexibility rather than the size of the pendent group is the determining factor in the glass transition properties of the styrene polymers.     

Alarm pheromone system of leaf-footed bugLeptoglossus zonatus (Heteroptera: Coreidae)

The alarm pheromone system ofLeptoglossus zonatus (Dallas) adults was shown to be composed of hexyl acetate, hexanol, hexanal, and hexanoic acid. Single components tested in the field elicited dispersive behavior of over 70% of adults. 2-(E)-Hexenal, found in the secretion of nymphs, but not in the exudates of adults, was also active against adults. In addition, first-instar nymphs responded to the four components of the alarm pheromone of adults as well as to 2-(E)-hexenal, a component of their own alarm pheromone system. Adults and nymphs possess different alarm pheromone systems, which are not specific to their own life stage. That hemipteran alarm pheromone systems are not species-specific was supported by the fact that both adult and nymphL. zonatus responded to butanoic acid, an alarm pheromone of Alydidae, which was not found in this Coreidae species.     

X-ray crystal structure of the dye 2-cyano-4-bromo-4′-N,N-diethylaminoazobenzene

The crystal structure and molecular conformation of 2-cyano-4-bromo-4′-N,N-diethylaminoazobenzene (C₁₇H₁₇N₄Br, mol. wt. = 357·2 a.m.u) has been determined from X-ray diffraction data; triclinic, P$\text{1}$ (No. 2), a = 10·132(11) Å, b = 12·216(16) Å, c = 6·966(11) Å, α = 104·21(9)°, β = 92·67(12)°, γ = 97·22(7)°, V = 826·5(9) ų, Z = 2, D_c = 1·436 g cm^?3, F(000) = 378, λ(MoKα) = 0·71069 Å, μ(MoKα) = 26·0 cm^?1. The structure was solved by the multiple solution direct method and refined by full-matrix least-squares to R = 0·059 for 1538 independent observed reflections. The azobenzene skeleton is planar to within 0·06 Å. Most significant bonding data are: NN, 1·290(8) Å; BrC, 1·866(6) Å; mean CN (azo) 1·380(8) Å; NNC, 113·6(4) and 115·3(4)°; NCC (cis relative to NN) 125·9(4)° and 126·7(4)°; NCC (trans) 116·8°(5)° and 116·1(4)°.