The monounsaturated acyl- and alkyl-moieties of wax esters and their distribution in commercial orange roughy (Hoplostethus atlanticus) oil

Wax esters were isolated from commercial orange roughy (Hoplostethus atlanticus) oil by column chromatography and fractionated by argentation thin layer chromatography. Following transesterification, the resultant fatty acid methyl esters and fatty alcohols were analyzed by gas chromatography. both acyl- and alkyl-moieties were mainly of the monoene structure within the 16∶1–22∶1 range. After derivatization, the positions of the double bonds of even numbered fatty acid and fatty alcohol isomers were located by chromatography-mass spectrometry and compared. Results of these positional analyses indicate that the primary desaturation reactions takes place in the Δ9 position of pre-existing (C₁₄ to C₂₄) acyl chains. It is proposed that acyl components from 18∶1 are subjected to chain elongation to form a mixture of 24∶1 isomers as the final product. Apart from the 24∶1 acyl moiety of the wax esters, in which the double bond was almost exclusively in the Δ15 position, de novo biosynthetic reactions on acids and alcohols appear to yield related acyl- and alkyl-moieties of resynthesized wax esters.     

Production of propylene glycol fatty acid monoesters by lipase-catalyzed reactions in organic solvents

Fatty acid monoesters of propylene glycol (1,2-propanediol) are good water-in-oil emulsifiers. These esters were synthesized enzymatically to overcome the problems associated with chemical processes. APseudomonas lipase was added to reaction mixtures containing propylene glycol and various acyl donors (fatty acids, fatty acid ethyl esters, fatty acid anhydrides and triglycerides) in organic solvents, and the mixtures were shaken at 30°C. The products were analyzed by gas chromatography. The yield of monoesters was affected by the acyl donors, organic solvents, temperature, water content, pH memory and reaction time. The anhydrous (lyophilized) enzyme and fatty acid anhydrides were best for monoester production. The optimum pH ranges were 4–5 and 8–10. The yields of propylene glycol monolaurate, monomyristate, monopalmitate, monostearate and monooleate with 50 mM fatty acid anhydrides as acyl donors were 97.2, 79.6, 83.7, 89.7 and 93.4 mM, respectively; those with 50 mM fatty acids as acyl donors were 37.3, 28.7, 28.7, 35.3 and 36.2 mM, respectively. The yields of propylene glycol monopalmitate, monostearate and monooleate with 50 mM triglycerides as acyl donors were 87.4, 65.1 and 83.2 mM, respectively.     

Sulfonated poly(ether ketone ketone) ionomers as proton exchange membranes

Sulfonated poly(ether ketone ketone) ionomers (SPEKK) with ion‐exchange capacities (IEC) between 0.2 and 3.4 meq/g were prepared by sulfonating PEKK with a mixture of concentrated and fuming sulfuric acids. Sulfonation occurs only on the phenyl rings attached to ether and ketone groups. The glass transition temperature of the dry SPEKK ionomers increased linearly with increasing IEC, and the ionomers were thermally stable to ～250°C, above which desulfonation occurred. Water‐swollen ionomers exhibited microphase separated morphologies, and the average correlation length determined by small angle X‐ray scattering increased with increasing IEC. The proton conductivity of hydrated SPEKK membranes measured by impedance spectroscopy ranged from ～10^–3 to 10^–1 S/cm as the IEC increased from ～1.0 to 2.4 meq/g. Single cell performance curves on membrane‐electrode assemblies (MEA) indicated that the SPEKK membranes approached the performance of Nafion? for an IEC of 2 meq/g. POLYM. ENG. SCI., 45:1081–1091, 2005. © 2005 Society of Plastics Engineers     

Identification of some volatile compounds in the odor of fecal pellets of the rabbit,Oryctolagus cuniculus

A study has been made of the volatile constituents in the vapors collected from fecal pellets of wild rabbits,Oryctolagus cuniculus. Measurements of changes in the heart rates of adult male rabbits exposed to the effluent of a gas chromatographic capillary column were used to indicate the presence of compounds which may be of behavioral significance. Combined with the use of high-resolution columns in gas chromatography and gas chromatography-mass spectrometry, this approach has implicated several classes of compounds, including volatile fatty acids and phenols, which in certain absolute or relative concentrations may be involved in the formation of signals of territorial importance.     

Fabrication of SiC-Whisker-Reinforced MoSi2 Composites by Tape Casting

In this paper, we describe a procedure for the processing of SiC-whisker-reinforced MoSi₂ composites via tape casting. Based on the characteristics of SiC whiskers and MoSi₂ powder in aqueous and nonaqueous solvents, a slip formulation (solvent, dispersant, binder, etc.) has been developed. The formulation developed allows for a uniform distribution of SiC whiskers in the matrix, easy separation of the tapes from the polymeric carrier, convenient control of both tape thickness and orientation of SiC whiskers, and a low binder burnout temperature. The latter is important for the prevention of the oxidation of MoSi₂ powder during the binder burnout in an oxidizing atmosphere.     

Melt characterization of ultra high molecular weight polyethylene using squeeze flow

A method for determining the melt viscosity and molecular weight of ultra high molecular weight polyethylene (UHMWPE) is described. The method, based on squeeze flow, was used to characterize seventeen UHM W-PE samples varying in molecular weight from 0.6 × 10⁶ to 5.1 × 10⁶ and in viscosity from 2.9 × 10⁶ to 3.4 × 10⁹ poise. A correlation between melt viscosity and molecular weight was demonstrated, but the reliability of a molecular weight determination decreased somewhat as molecular weight increased. As a predictor of melt processability, the method provides the speed and simplicity heretofore lacking in UHMW-PE characterization by solution viscosity while retaining high reproducibility.     

Studies of polymer–polymer solubility using a two-dimensional solubility parameter approach

The two-dimensional solubility parameter approach has been applied to the prediction of solubility of one polymer in another. The solubility parameters of a number of polymers have been calculated and the second dimension shown to improve the agreement between the calculated solubility and that measured using a ternary solution technique. The method proved most useful for predicting the effect of small structural modifications on solubility, and several examples of changing solubility, monitored by calculations and measurements, are given. Structural modifications included copolymer ratio variations and substitutions to affect polymer density or reduce polarity of functional groups. The effects of temperature and molecular weight on solubility are discussed in terms of regular solution theory, which could not account for the decrease in solubilities with increased temperature observed for several polymer–polymer systems.     

Evaluating the 1931 CIE color‐matching functions

The use of colorimetry within industry has grown extensively in the last few decades. Central to many of today's instruments is the CIE system, established in 1931. Many have questioned the validity of the assumptions made by Wright¹ and Guild,² some suggesting that the 1931 color‐matching functions are not the best representation of the human visual system's cone responses. A computational analysis was performed using metameric data to evaluate the CIE 1931 color‐matching functions as compared to with other responsivity functions. The underlying assumption was that an optimal set of responsivity functions would yield minimal color‐difference error between pairs of visually matched metamers. The difference of average color differences found in the six chosen sets of responsivity functions was small. The CIE 1931 2° color‐matching functions on average yielded the largest color difference, 4.56 ΔE. The best performance came from the CIE 1964 10° color‐matching functions, which yielded an average color difference of 4.02 ΔE. An optimization was then performed to derive a new set of color‐matching functions that were visually matched using metameric pairs of spectral data. If all pairs were to be optimized to globally minimize the average color difference, it is expected that this would produce an optimal set of responsivity functions. The optimum solution was to use a weighted combination of each set of responsivity functions. The optimized set, called the Shaw and Fairchild responsivity functions, was able to reduce the average color difference to 3.92 ΔE. In the final part of this study a computer‐based simulation of the color differences between the sets of responsivity functions was built. This simulation allowed a user to load a spectral radiance or a spectral reflectance data file and display the tristimulus match predicted by each of the seven sets of responsivity functions. © 2002 Wiley Periodicals, Inc. Col Res Appl, 27, 316–329, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/col.10077     

Modification of Piezoelectric Characteristics of the Pb(Mg,Nb)O3-PbZrO3-PbTiO3 Ternary System by Aliovalent Additives

The effects of donor and acceptor doping on the piezoelectric properties of 18Pb(Mg_1/3Nb_2/3)O₃·39PbZrO₃·43PbTiO₃ternary solid solution have been investigated. The dopants influence in a pronounced way both the crystal structure and microstructure of the materials. The materials are transformed from the rhombohedral to the tetragonal structure, and the grain size is reduced when Nb ⁵⁺ cations are added. The crystal structures are transformed from the rhombohedral to the cubic structure, and grain growth is enhanced, when Mg ²⁺ cations are included. The values of K _P and K are maximized for 1-mol%-Nb⁵⁺-doped samples (K _P= 0.69, K = 1152); the Q _m factor and E _c are optimized for 4-mol%-Mg²⁺-doped samples ( Q _m= 1534, E _c= 0.56).     

Development of optical anisotropy in vitrains during carbonization

The purpose of this work was to examine the possible significance in the formation of metallurgical coke of the anisotropic spherical mesophase exemplified by that found during the carbonization of pitch-like materials, and to ascertain if the various types of optical anisotropy found in coke could form a basis for the characterization of cokes produced from different coals. Vitrains from a wide range of coals were carbonized at temperatures from 370 to 1000 °C and the types and amounts of optical anisotropy in the resulting semi-cokes and cokes were determined from microscopic examination, the anisotropic components being classified according to grain size of the granular mosaics and appearance. The anisotropy developed directly from the isotropic phase, appearing initially as a fine-grained mosaic. With increasing carbonization temperature, this fine-grained mosaic was transformed into progressively coarser-grained anisotropy, the extent of this transformation depending on the rank of the vitrain. It is therefore concluded that the formation, growth and coalescence of anisotropic spherical bodies, such as occurs during the carbonization of pitch, is not a necessary precursor of the mosaic anisotropy in coke. The type and amount of anisotropy developed provide a quantitative means of characterising different cokes.