NMR chemical shift reagents in structural determination of lipid derivatives: II. Methyl petroselinate and methyl oleate

Whentris(1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octaneodionato)europium (III)—Eu(fod)₃—forms a complex with a sufficiently basic functional group in a donor molecule, the change in the magnetic environment of protons near the coordination site causes their nuclear magnetic resonance (NMR) signals to shift to different positions. Consequently Eu(fod)₃ and other compounds that similarly affect NMR signals have been designated chemical shift reagents (csr). Because of their ability to shift proton signals, csr substantially increase the amount of structural information that can be obtained from NMR spectroscopy, frequently converting complicated splitting patterns into first-order spectra. Some generally useful experimental and interpretive csr techniques are described here using methyl petroselinate and methyl oleate as examples. Csr studies of methyl petroselinate reveal that the position of the double bond is at C-6, and that there is no chain substitution or branching before C-9. Csr studies of methyl oleate reveal that the position of the double bond is at or beyond C-9, and that there is no chain substitution or branching before C-6. Some suggestions are presented for expanding the amount of structural information that can be obtained by csr studies of unsaturated lipid derivatives. Presented in part at AOCS Meeting, Atlantic City, October, 1971.     

Esters of hydroxystearic acids as primary low-temperature plasticizers for a vinyl chloride—Vinyl acetate copolymer

Summary Thirty-one acyloxy or aryloxy esters prepared from hydroxystearic acids have been evaluated as plasticizers for a vinyl chloride-vinyl acetate copolymer (95∶5). Many of them were found to be primary plasticizers, having outstanding low-temperature performance when employed at the 35% level. Formulations with these compounds compared quite favorably in tensile properties with those containing the di-2-ethylhexyl esters of phthalic, sebacic, azelaic, and adipic acids. Volatility losses were similar to those of the four di-2-ethylhexyl esters. The loss of plasticizer through migration was equal to or less than that from compositions containing the esters of sebacic, azelaic, and adipic acids but was greater than that of the phthalate ester. A mechanistic scheme of plasticizer-polymer interaction has been presented, proposing that the rate of diffusion of plasticizer through the polymer mass is a controlling factor in both good low-temperature performance and the resulting high migration losses. Methyl esters, some aromatic esters, and esters containing three or more polar centers have improved permanence but show a more rapid change in torsional modulus as the temperature is lowered during the determination of the Clash-Berg stiffening temperature. Eastern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

EXTERNAL FLUID HEATING OF A POROUS ED

This work deals with the thermal analysis of externally heated porous beds of finite length. A one dimensional model was developed that includes conduction and storage in both the fluid and bed, convective exchange between the fluid and bed, and the effect of adsorption/desorption in the bed. This model results in two coupled differential equations for the fluid and bed temperatures as functions of four independent dimensionless parameters. These equations were solved numerically using finite difference approximations. A truncation error analysis was carried out to maintain an accurate solution. The method of normalization is such that the results of this analysis are of use in bed design when the breakthrough characteristics in finite length beds are of interest. A method to measure bed thermal performance is defined and a means to optimize bed thermal performance is presented. An experiment was conducted to validate the numerically obtained results. A comparison of numerical to experimental results is presented     

2-Methylthiazolidine and 4-ethylguaiacol,male sex pheromone components of the cockroachNauphoeta cinerea (dictyoptera,blaberidae): A reinvestigation

InNauphoeta cinerea, male calling behavior is associated with sex pheromone release by the sternal glands. The male pheromone that attracts females from a distance is a mixture of 2-methylthiazolidine and 4-ethylguaiacol. It is active at very low concentrations, 0.05 and 0.01 ng, respectively. Two other compounds, 3-hydroxy-2-butanone and 2-methyl-2thiazoline, act at close range, keeping the female in the vicinity of the male. The function of the volatile pheromone and those of previously described contact pheromones are discussed in regard to their possible involvement in the establishment of male dominant-subordinate relationships.     

Synthesis and Microstructure of Highly Oriented Lead Titanate Thin Films Prepared by a Sol-Gel Method

Thin films of PbTiO₃ were deposited on fused silica, resistor-grade alumina, and single-crystal (100) MgO by a sol–gel processing method. Whereas the films deposited on silica and alumina substrates were randomly oriented and polycrystalline, highly {100} oriented PbTiO₃ films were grown on the MgO single crystals. The perovskite-type structure was observed with films deposited on the single-crystal MgO and annealed at temperatures as low as 470°C, whereas a pyrochlore-type strcuture was observed with films on fused silica and alumina processed in a similar manner. All films heat-treated at temperatures in excess of 570°C showed significant formation of a second PbTi₃O₇ phase. The films were characterized by electron microscopy and glancing-incidence-angle X-ray diffraction.     

Dose and enantiospecific responses of white pine cone beetles,Conophthorus coniperda,to alpha-Pinene in an eastern white pine seed orchard

The white pine cone beetle, Conophthorus coniperda, exhibited dose and enantiospecific responses to -pinene in stands of mature eastern white pine, Pinus strobus, in a seed orchard near Murphy, North Carolina, USA. (–)--Pinene significantly increased catches of cone beetles to traps baited with (± )-trans-pityol. (+)--Pinene did not increase catches of beetles to pityol-baited traps and interrupted the response of beetles to traps baited with (±)-trans-pityol and (–)--pinene. Maximal attraction of cone beetles to pityol-baited traps was obtained with lures releasing (–)--pinene at a rate of 103 mg/day at 23^°C. Lures releasing (–)--pinene at rates lower or higher than 103 mg/day resulted in reduced catches to traps baited with (±)-trans-pityol. The sex ratio in all catches was heavily male biased. Attraction of the clerid predator, Thanasimus dubius, to traps baited with (±)-trans-pityol increased significantly with the presence of -pinene, irrespective of enantiomeric composition. Maximal attraction of T. dubius to pityol-baited traps occurred with devices releasing (–)--pinene at the highest rate tested, 579 mg/d at 23^°C, a sub optimal rate for cone beetles.     

Processing of mesocarbon microbeads to high-performance materials: Part II. Reaction bonding by in situ silicon carbide and nitride formation

The processing of carbon-ceramic composites by utilizing the unique sintering ability of mesocarbon microbeads (MCMB) is reported. The ceramic constituents (silicon nitride and silicon carbide) are formed in situ by reactions between MCMB and silicon in different atmospheres. In comparison with direct addition of ceramic (SiC, Si₃N₄) phases, in situ formation shows several appealing features. By inducing the reaction of silicon with MCMB, the sintering ability of the composite is enhanced via reaction bonding mechanisms. Similarly, it is demonstrated that composite porosity is limited owing to silicon reaction with nitrogen. The reactive formation of nanoscale ceramic reinforcements via decomposition of the silicon-containing polymer (e.g. poly-carbomethyl-silane) is also reported. This approach results in formation of uniform nanosized (>100 nm) SiC layers strongly bonded to the surface of the carbon particles. The presented results contribute to the development of carbon-ceramic materials with high-operational properties.     

Water flux,DSC, and cytotoxicity characterization of membranes of cellulose acetate produced from sugar cane bagasse,using PEG 600

Summary In this article, cellulose acetate produced through the homogeneous acetylation of sugar cane bagasse cellulose was used to produce membranes, using poly(ethyleneglycol) 600 (PEG 600) as an admixture. The membranes were characterized using water flux measurements (Payne’s cup), differential scanning calorimetry (DSC) and neutral red uptake (cytotoxicity). The results showed that PEG 600 acts as a crystallinity inductor and/or pore former in the cellulose acetate matrix. The induction of crystallinity is important for this system since it had not been reported on the literature yet. The results also demonstrated that the studied membranes present a nontoxic behavior.     

Tissue-type plasminogen activator variants with domain duplications and rearrangements

The interactions between tPA domains that are important forcatalysis are poorly understood. We have probed the functionof interdomain interactions by generating tPA variants in whichdomains are duplicated or rearranged. The proteins were expressedin a transient mammalian expression system and tested in vitrofor their ability to activate plasminogen, induce fibrinolysisand bind to a forming fibrin clot. Duplication of the heavychain domains of tPA produced enzymatically active tPA variants,many of which demonstrated similar in vitro amidolytic and fibrinolyticactivity and similar fibrin affinity to the parent molecule.Zymographic analysis of the domain duplication tPA variantsshowed one major active species for each variant. Selectionof the residues duplicated and the interdomain spacing werefound to be critical considerations in the design of tPA variantswith duplicated domains. We also rearranged the domains of tPAsuch that kringle 1 replaced the second kringle domain and viceversa. An analysis of these variants indicates that the firstkringle domain can confer fibrin affinity to a tPA variant andfunction in place of kringle 2. Therefore, in wild-type tPA,the functions of kringle 1 and kringle 2 must be dependent partiallyon their orientation within the heavy chain of the protein.The functional autonomy of the heavy and light chains of tPAis demonstrated by the activity of a tPA variant in which theorder of the heavy and light chains was reversed.