Stability of Fe3+ — VO defect pairs in polycrystalline Pb(Ti,Zr)O3

The intensity of the EPR signal with g = 5.985 arising from a ferric ion — oxygen vacancy defect pair (Fe³⁺ — V_O) in PbTiO₃, varies with the extent of PbO nonstoichiometry at constant Fe³⁺ content due to an increased oxygen vacancy concentration. In PZT solid solutions, the signal intensity decreases with an increase in Zr. A lower intensity is also noticed for Fe³⁺ — V_O signals in PbZrO₃. This behaviour is explained on the basis of PbO nonstoichiometry arising from independent Pb- and O-vacancies as well as the randomly distributed crystallographic shear (CS) plane defects. The contribution to PbO nonstoichiometry from CS planes is larger in high zirconium compositions of PZT.     

Evidence for a catabolic role of glucagon during an amino acid load

Despite the strong association between protein catabolic conditions and hyperglucagonemia, and enhanced glucagon secretion by amino acids (AA), glucagon's effects on protein metabolism remain less clear than on glucose metabolism. To clearly define glucagon's catabolic effect on protein metabolism during AA load, we studied the effects of glucagon on circulating AA and protein dynamics in six healthy subjects. Five protocols were performed in each subject using somatostatin to inhibit the secretion of insulin, glucagon, and growth hormone (GH) and selectively replacing these hormones in different protocols. Total AA concentration was the highest when glucagon, insulin, and GH were low. Selective increase of glucagon levels prevented this increment in AA. Addition of high levels of insulin and GH to high glucagon had no effect on total AA levels, although branched chain AA levels declined. Glucagon mostly decreased glucogenic AA and enhanced glucose production. Endogenous leucine flux, reflecting proteolysis, decreased while leucine oxidation increased in protocols where AA were infused and these changes were unaffected by the hormones. Nonoxidative leucine flux reflecting protein synthesis was stimulated by AA, but high glucagon attenuated this effect. Addition of GH and insulin partially reversed the inhibitory effect of glucagon on protein synthesis. We conclude that glucagon is the pivotal hormone in amino acid disposal during an AA load and, by reducing the availability of AA, glucagon inhibits protein synthesis stimulated by AA. These data provide further support for a catabolic role of glucagon at physiological concentrations.     

Thermal analysis of polymer–water interactions and their relation to gas hydrate inhibition

Gas hydrates formed in oil production pipelines are crystalline solids where hydrocarbon gas molecules such as methane, propane, and their mixtures are trapped in a cagelike structure by hydrogen‐bonded water molecules to form undesirable plugs. Methanol and glycol are currently used to prevent these plugs via thermodynamic inhibition. Small amounts of water‐soluble polymers may provide an alternate approach for preventing gas hydrates. In this study, we expand the fundamental understanding of water–polymer systems with differential scanning calorimetry. Nonfreezable bound water was used to quantify polymer–water interactions and relate them to the chemical structure for a series of polymers, including acrylamides, cyclic lactams, and n‐vinyl amides. For good interactions, the water structure needs to be stabilized through hydrophobic interactions. An increased hydrophobicity of the pendant group also appears to favor polymer performance as a gas hydrate inhibitor. Good inhibitors, such as poly(diethyl acrylamide) and poly(N‐vinyl caprolactam), also show higher heat capacities, which indicate higher hydrophobicity, than poor performers such as polyzwitterions, in which hydrophilicity dominated. The phase behavior and thermodynamic properties of dilute polymer solutions were also evaluated through measurements of the heat of demixing and lower critical solution temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2642–2653, 2007     

Mechanistic Insight in the Ethane Dehydrogenation Reaction over Cr/Al2O3 Catalysts

A Cr/Al₂O₃ alkane dehydrogenation catalyst exhibits a maximum in ethylene yield during an ethane dehydrogenation cycle. Isotopic labelling experiments with monolabelled ¹³C-ethane and deuterium were used to elucidate whether the initial activity increase could be due to formation of an active, larger hydrocarbon intermediate on the surface. The results strongly indicate that this is not the case, and instead point to a traditional reaction cycle involving adsorption of ethane to form an ethyl species, followed by desorption of ethene and hydrogen. Transient kinetic data suggest that ethane adsorption is the rate-determining step of reaction.     

2,2′-oxo-1,1′-azobenzene: microbial transformation of rye (Secale cereale L.) allelochemical in field soils byAcinetobacter calcoaceticus: III

Acinetobacter calcoaceticus, a gram-negative bacterium isolated from field soil, was found to be responsible for the biotransformation of 2(3H)-benzoxazolinone (BOA) to 2,2-oxo-1,1-azobenzene (AZOB). Experiments were conducted to evaluate the transformation of BOA to AZOB by this microbe in sterile and nonsterile soil. Transformation studies with soils inoculated withA. calcoaceticus indicated that the production of AZOB increased linearly with the concentration of BOA in sterile soil and showed a quadratic trend in nonsterile soils. This also indicated that all soil types studied for the transformation experiments might containA. calcoaceticus capable of the conversion of benzoxazolinones.     

Ageing studies of pineapple leaf fiber–reinforced polyester composites

This experimental study evaluated the water absorption characteristics of pineapple leaf fiber (PALF)–polyester composites of different fiber content. The degree of water absorption was found to increase with fiber loading. The mechanism of diffusion was analyzed and the effect of fiber loading on the sorption kinetics was studied. The diffusion coefficient was calculated and found to increase with fiber content. Studies were also made to correlate water absorption with the cross‐sectional areas of the specimens. The effects of ageing on the tensile properties and dimensional stability of PALF polyester composites were studied under two different ageing conditions. Ageing studies showed a decrease in tensile strength of the composites. The composite specimens subjected to thermal ageing showed only a slight deterioration in strength. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 503–510, 2004     

Zero-<Emphasis Type="Italic">trans</Emphasis> shortening using palm stearin and rice bran oil

Several pilot-scale trials reported in this paper, using palm stearin-rice bran oil (PS-RBO) blends, obviously did not contain trans FA (TFA), whereas the commercial products were found to contain 18–27% TFA. The effects of processing conditions such as rate of agitation, crystallization temperature, and composition of the blends on the crystal structure of shortenings were studied. The products were evaluated for their physicochemical characteristics using DSC, X-ray diffraction (XRD), HPLC, and FTIR techniques. The formulation containing 50% PS and 50% RBO showed melting and cooling characteristics similar to those of hydrogenated commercial “vanaspati” samples. Analysis of the FA composition revealed that the formulated shortenings contained 15–19% C_18∶2 PUFA. Tocopherol and tocotrienol contents of the experimental shortenings were in the range of 850–1000 ppm with oryzanol content up to 0.6%. XRD studies demonstrated that the crystal form in the shortenings was predominantly the most stable β′ form, and there was less of the undesirable β form.     

Lipid metabolism of acetate-1-14C by leukocytes from dogs fed an arteriosclerosis-inducing diet

Dogs were maintainedoon a control ration or on a semisynthetic diet, containing 5% cholesterol and 16% hydrogenated coconut oil, known to induce hyperlipemia and arteriosclerosis. Circulating leukocytes isolated from dogs fed the coconut oil containing diet were shown to incorporate 50% more radioactivity into lipids than control leukocytes when incubated with acetate-1-¹⁴C. This increase, expressed as dpm/mg of leukocyte DNA, was not specific for any particular lipid since the distribution of radioactivity between neutral lipids and phospholipids, as well as among their subfractions, was the same regardless of the diet fed. The labeling patterns observed suggest that leukocyte fatty acid synthesis from acetate occurs predominantly, and perhaps exclusively, by the chain elongation pathway.     

Oxidation and Fracture Strength of High-Purity Reaction-Bonded Silicon Nitride

Reaction-bonded Si₃N₄ (RBSN) made from high-purity Si powder is unusually resistant to degradation caused by exposures to air for up to 50 h at temperatures up to 1400°C. The weight gain during oxidation of this SiH₄-originating RBSN is approximately 10 times less than conventional RBSN. Contrary to normally observed strength degradations, room-temperature strengths of this high-purity, oxidized RBSN (avg = 435 MPa, max. = 668 MPa) remained at their unusually high, as-processed levels after 1000° and 1400°C oxidizing exposures. Fracture toughness values were unaffected by oxidation ( K _IC= 2.3 to 2.4 MPa · m^1/2). This superior oxidation resistance results from the high purity and the small diameter pore channels (0.01 to 0.06 μm) achieved in this SiH₄-originating RBSN.