Revisiting the addition reaction of TeCl4 to alkynes: the crystal structure and docking studies of 1-chloro-2-trichlorotelluro-3-phenyl-propen-2-ol

Tellurium tetrachloride adds to alkynes via two pathways: a concerted syn addition, that yields Z-tri- and tetra-substituted alkenes or by an anti addition that yields E-alkenes. The mechanistic aspects of these divergent pathways have been reevaluated at the light of crystallographic data. The molecules, of the title compound, in the crystal, are associated in a helical fashion with a Te...Te pitch of 6.3492(6) angstrom. As it exhibits inhibitory activity for cathepsin B and in order to gain more insight of the inhibition mechanism, a docking study was undertaken providing insight on why organic telluranes are more efficient inhibitors than inorganic ones as AS-101. (c) 2006 Elsevier B.V. All rights reserved.

EFFECT OF THE ADDITION OF CR AND NB ON THE MICROSTRUCTURE AND ELECTROCHEMICAL CORROSION OF HEAT-TREATABLE AL-ZN-MG ALLOYS

The effect of the addition of Cr and Nb on the microstructure and the electrochemical corrosion of the weldable, high-strength and stress corrosion cracking (SCC) resistant Al-5%Zn-1.67%Mg-0.23%Cu alloy (H) has been studied. Combined additions of the alloying elements, J (with Nb), L (with Cr) and O (with Cr and Nb) and different heat treatments, ST (cold-rolled), A (annealed), F (quenched), B (quenched and aged) and C (quenched in two steps and aged), to obtain different microstructures and hardness have been performed. To correlate the electrochemical corrosion with the microstructure of the specimens, corrosion potential (E(cor)) measurements in different chloride solutions were performed and optical microscopy, SEM, TEM and EDX were applied. In chloride solutions containing dissolved O-2 or H2O2, the present alloys were polarized up to the pitting attack. It was shown that the E(cor) measurements were very sensitive to the alloy composition and heat treatment, increasing in the order H < J < L < O < Al (for a given heat treatment) and F < A approximate to ST < B < C (for a given alloy). The MgZn2 precipitates of the annealed (A) and cold-rolled (ST) specimens were dissolved in chloride solutions containing oxidizing agents and pitting attack was shown to develop in the cavities where the precipitates were present. In the specimens B and C, the compositions of the precipitate free zones was found to be equal to that of the matrix solid solution and preferential intergranular attack was not evident, this being in agreement with their SCC resistance. The addition of Cr and Nb increased the pitting corrosion resistance. The effects of Cr and Nb were additive, that of Cr being predominant, either, in the E(cor) shift or in the increase in the pitting corrosion resistance.

Effect of addition of MTES on the structure of siloxane-PPG nanocomposites

Hybrid transparent and flexible siloxane-polypropyleneglycol (PPG) materials with covalent bonds between the inorganic (siloxane) and organic (polymeric) phases were prepared by sol-gel process. In order to improve the quality of the mechanical properties of these materials, different amounts of methyltriethoxysilane (MTES) were added to the initial sol. The effect of MTES addition on the structure of the composites was studied by Small-Angle X-Ray Scattering (SAXS) and Si-29 Nuclear Magnetic Resonance (Si-29 NMR). In absence of MTES, SAXS spectra exhibit a peak that is assigned to spatial correlation due to short range order between the siloxane clusters embedded in the polymeric phase. The experimental results indicate that, for low MTES concentrations ([MTES]/[O] less than or equal to 0.8, O: ether-type oxygen of PPG), the silicon species resulting from hydrolysis and condensation of MTES fill the open spaces between polymeric chains, interacting with the ether-type oxygens. For larger MTES content ([MTES]/[O] greater than or equal to 0.8), the number of free ether-type oxygen sites avalaible for reaction with such silicon species is not large enough. Consequently, a fraction of silicon species resulting from MTES addition graft to siloxane clusters formed by hydrolysis and condensation of the hybrid precursor. For all MTES concentrations the condensation degree of the siloxane phase, determined from Si-29 NMR spectroscopy, is high (> 69%), as expected under neutral pH synthesis conditions.

Novel stereoselective addition of some nucleophiles to 2,3-bis(methylsulfanyl) norbornenobenzoquinone

2,3-Bis(methylsulfanyl)norbomenobenzoquinone undergoes reaction with nitrogen, oxygen, sulfur or carbon nucleophiles to give the trisubstituted adducts containing the new substituent at the ring junction. Their configurations are assigned by H-1 NMR spectroscopy and NOE enhancement experiments. (C) 1997 Elsevier B.V. Ltd.

The acid-base impact of free water removal from, and addition to, plasma

Water, compared with plasma at a pH of 7.4, is a weak acid. The addition of free water to a patient should have an acidifying effect (dilutional acidosis) and the removal of it, an alkalinizing effect (concentrational alkalosis). The specific effects of free water loss or gain in a relatively complex fluid such as plasma has, to the authors' knowledge, not been reported. This information would be useful in the interpretation of the effect of changes in free water in patients. Plasma samples from goats were either evaporated in a tonometer to 80% of baseline volume or hydrated by the addition of distilled water to 120% of baseline volume. The pH and partial pressure of carbon dioxide, sodium, potassium, ionized calcium, chloride, lactate, phosphorous, albumin, and total protein concentrations were measured. Actual base excess (ABE), standard bicarbonate, anion gap, strong ion difference, strong ion gap, unmeasured anions, and the effects of sodium, chloride, phosphate, and albumin changes on ABE were calculated. Most parameters changed 20% in proportion to the magnitude of dehydration or hydration. Bicarbonate concentration, however, increased only 11% in the evaporation trial and decreased only -2% in the dehydration trial. The evaporation trial was associated with a mild, but significant, metabolic alkalotic effect (ABE increased 3.2 mM/L), whereas the hydration trial was associated with a slight, insignificant metabolic acidotic effect (ABE decreased only 0.6 mM/L). The calculated free water ABE effect (change in sodium concentration) was offset by opposite changes in calculated chloride, lactate, phosphate, and albumin ABE effects.

Sintering mechanisms of ZrO2 center dot MgO with addition of TiO2 and CuO

Substitutions of Ti and Cu in ZrO2.MgO (Z), cause transformation from monoclinic (m) to cubic (c) and tetragonal (t). According to the vacancy model and solid Solution formation models, neither CuO nor TiO2 cause zirconia stabilization, which derives front other phenomena. Data analysis by TMA using the CRH (constant rate of heating) method shows a solid state reaction of ZrO2.MgO.TiO2 (Z.TiO2) demonstrating a dominant mechanism of volume diffusion (n = 1). However, the sintering of ZrO2.MgO.CuO (Z.CuO) shows a viscous flow mechanism (n = 0), a similar phenomena to that of by sintering of glass. Transformations, such as: CuO to Cu2O at 1000 degreesC, ZrO2 (m) to ZrO2 (t) at 1100 degreesC and Cu2O (s) to Cu2O (l) at 1230 degreesC cause successive rearrangements of microstructure inside of region I (sintering process) and lead to interpretation errors when the Bannister equation is used. (C) 2003 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Non-ventilation during early incubation in combination with dexamethasone administration during late incubation: 1. Effects on physiological hormone levels, incubation duration and hatching events

This study investigated the effect of non-ventilation of the incubator during the first 10 days of incubation and its combination with dexamethasone administration at day 16 or 18 of incubation on hatching parameters and embryo and post-hatch chick juvenile physiology. A total of 2400 hatching eggs produced by Cobb broiler breeders were used for the study. Blood samples were collected at day 18 of incubation, at internal pipping stage (IP), at the end of hatch (day-old chick) and at 7-daypost-hatch for T-3, T-4 and corticosterone levels determination. From 448 to 506 h of incubation, the eggs were checked individually in the hatcher every 2 h for pipping and hatching. The results indicate that non-ventilation during the first 10-day shortened incubation duration up to IP, external pipping (EP) and hatch, had no effect on hatchability and led to higher T-3 levels at IP but lower corticosterone levels at 7-day-post-hatch. The injection of dexamethasone at days 16 and 18 of incubation affected hatching and blood parameters in both the ventilated and non-ventilated embryos differentially and the effect was dependent on the age of the embryo. Dexamethasone increased T-3 levels and T-3/T-4 ratios but the effect was greater with early non-ventilation of eggs. Dexamethasone decreased hatchability but the effect was greater when injected at day 16 and especially in ventilated embryos. The effects of incubation protocols and dexamethasone treatments during incubation were still apparent in the hatched chicks until 7 days of age. The changes in T-3, T-4 and corticosterone levels observed in response to the early incubation conditions and late dexamethasone treatments in this study suggest that incubator ventilation or non-ventilation may influence the hypothalamic-pituitary-adrenal axis (HPA) regulation of stress levels (in terms of plasma corticosterone levels) and thyroid function in the embryo with impact on incubation duration, hatching events and early post-hatch life of the chick. Our results also suggest that some stages of development are more sensitive to dexamethasone administration as effects can be influenced by early incubation protocols. (c) 2006 Elsevier B.V. All rights reserved.

Influence of the addition of antioxidants in vivo on the fatty acid composition of fish fillets

In this study, the influence of the addition of antioxidants in vivo on the fatty acid composition of the flesh of a freshwater fish known as pacu (Piaractus mesopotamicus) is verified. Four groups (one being the control group) of juvenile pacu were cultured on isocaloric and isoproteic diets. The lipid source was soybean oil and diets were added with either 100 ppm of alpha-tocopheryl acetate, or 100 ppm of BHT or 1.4 g of rosemary extract (Herbalox(R))/kg diet. The fatty acid composition of the lipids of the different groups was determined before and after irradiation at 2 and 3 kGy, respectively, for the evaluation of the protective effects of the different antioxidants. Similarly, thiobarbituric acid reactive substances (TBARS) were determined from irradiated and nonirradiated samples. The results showed that the use of antioxidants altered the fatty acid composition of the fillets. TEARS and irradiation confirmed their important role in protecting against lipid oxidation. Among all the antioxidants used, tocopherol was the most efficient, as shown by the highest percentage of polyunsaturated fatty acids (PUFA), by the lowest values of TEARS and by the analyses of the individual fatty acid levels at different irradiation doses. Significant statistical differences were observed only in 17% of the fatty acids in the fillets of the groups. (C) 1999 Elsevier B.V. Ltd. All rights reserved.

Correlation between acidic ninhydrin and HPLC methods to evaluate fraudulent addition of whey in milk

The acidic ninhydrin spectrophotometric method (ANSM) for quantitative determination of free and bound sialic acid of milk glycoprotein has been proved to be fast and efficient for routine detection of fraudulent addition of rennet whey to fluid milk. In this research the ANSM was compared with the high performance liquid chromatography (HPLC) method, internationally recommended for caseinomacropeptide (CMP) determination, which besides its high accuracy is more sophisticated and requires trained personnel. For several sample conditions (raw milk and milk with variable added amounts of rennet cheese whey), the methods showed an excellent linear correlation, with r = 0.981 when milk was deproteinized with a 120 g.L-1 final concentration of trichloroacetic acid (TCA) concentration. The best correlations could be seen with final concentrations of 100 g.L-1 and 80 g.L-1 TCA; respectively, r = 0.992 and 0.993.

Effect of the addition of ZnO seeds on the electrical proprieties of ZnO-based varistors

ZnO has the characteristic of presenting an intermediate value for the effective 3 eV barrier at room temperature. ZnO ceramics are applied in high-voltage systems or circuits. Attempts were made to reduce the number of effective barriers in the system by adding large particles of ZnO to the varistor composition. This procedure reduced the breakdown field of the varistors by values up to 90% lower than those initially obtained, and produced nonlinear coefficients as low as 20. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Sensitivity of SnO2 non-ohmic behavior to the sintering process and to the addition of La2O3

The work reported here consisted of a study of the sensitivity of the nonlinear electrical properties of dense SnO2. CoO ceramic systems to low concentrations of La2O3, sintering temperature and cooling rates. The nonlinear electrical properties of these systems were found to increase with decreasing cooling rates, a behavior attributed to the CoO solid state reactions at temperatures below 1000 degreesC. Post-annealing treatment in N-2-rich atmospheres strongly decreases the non-ohmic behavior of SnO2. CoO ceramic systems. However, this behavior may be restored through thermal treatment in an O-2-rich atmosphere. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

The effect of timing of thermal conditioning during incubation on embryo physiological parameters and its relationship to thermotolerance in adult broiler chickens

Previously, we reported that thermal conditioning at 39degreesC on days 13-17 of incubation of broiler eggs enabled thermotolerance during post-hatch growth (J. Therm. Biol. 28 (2003) 133). Tolerance to a temperature of 30degreesC was accompanied by changes in thyroid hormones and metabolic parameters. In the current study, we determined the mechanism of epigenetic heat adaptation during embryonic age by measuring blood physiological parameters that may be associated with the ultimate effects of thermal conditioning. Hatching eggs from Ross breeders were subjected to heat treatment of 39degreesC at days 13, 14, 15, 16 and 17 of incubation for 2 h per day. Control eggs were incubated at 37.6degreesC. Samples of eggs were withdrawn on each day of thermal conditioning and at internal pipping (IP) to obtain blood samples from embryos. The remaining eggs were weighed at day 18 and transferred to hatchers. The timing of IP, external pipping (EP) and hatching were monitored every 2 h. At hatch, chicks were weighed and hatchability was determined. Blood samples were obtained from samples of day-old chicks. T3, T4, corticosterone, pCO(2), pO(2) levels were determined in the blood. Blood pH was measured and T3/T4 ratios were calculated. Heat conditioning significantly increased corticosterone and pO(2) levels and blood pH but depressed pCO(2) at day 14. These were followed by a significant depression of T4 level on day 15. Remarkably, at day 16, all these parameters were back to normal as in the control embryos. Hatching was delayed by thermal conditioning probably as a result of the depressed corticosterone levels at IP. Hatchability was also lower in the heat-treated group but 1-day old chick weights were comparable to those of the controls. The result suggests that epigenetic thermal conditioning involves changes in these physiological parameters and probably serve as a method for epigenetic temperature adaptation since the same mechanisms are employed for coping with heat during post-embryonic growth. It also suggests that days 14-15 may be the optimal and most sensitive timing for evoking this mechanism during embryonic development. The adverse effects of heat treatment observed in this study may have been due to the continued exposure to heat until day 17. Fine-tuning thermal conditioning to days 14-15 only may improve these production parameters. (C) 2003 Elsevier Ltd. All rights reserved.