Biochemical,functional, and histochemical effects of essential fatty acid deficiency in rat kidney

The present study was designed to examine the effects of EFA deficiency (EFAD) on biochemical, functional, and structural aspects of the kidney in growing and adult rats fed a normal or EFAD diet for 9 wk after weaning. Food and fluid intake (FI), urine volume, and Na⁺ and K⁺ excretions were measured weekly from weeks 4 to 8 by placing the rats in individual metabolic cages for 24 h. At week 9, Li⁺ and a 5% water load, respectively, were administered at 14 and 1.5 h prior to glomerular and proximal tubular function studies, as assessed by 3-h creatinine (C_Cr) and Li⁺ (C_Li+) clearances. Hematocrit and urine volume; serum and urine [Cr], [Li⁺], [Na⁺], and [K⁺]; and renal FA distribution were also measured. Data [corrected to 100 g/body weight (bw) and presented as means ±SEM] were significant, at P<-0.05. Despite a similar ingestion of solids from weeks 4 to 7 (weeks 7 to 10 of life), the rats on the EFAD diet showed a decreased body weight from week 5. From weeks 4 to 8, Fl and urine volume were similar for both groups, but the Fl increased at week 6 in the EFAD group; 24-h Na⁺ and K⁺ excretions were similar at all weeks, except for an increase in the EFAD group for both ions at week 7. In the EFAD group, C_Cr and C_Li+ decreased by 27 and 56.3%, respectively (385.7±33.4 vs. 280±21.1, and 21.0±2.1 vs. 9.2±1.1 μL/min/100 g; n=9 vs. 10), the latter result suggesting increased proximal reabsorption. The 3-h Na⁺ and K⁺ excretions were similar, but the Li⁺ decreased (0.78±0.06×10⁻² vs. 0.32±0.03×10⁻² μeq/min/100 g) in the EFAD group, giving additional support to the suggestion. Renal structure was normal and similar for both groups, but the EFAD group showed a more prominent proximal tubule brush border, together with heavier periodic acid-Schiff staining in all specimens from weeks 5 to 9. In the EFAD group, FA of the n−9 and n−7 series were higher, but most of the n−6 series were lower as a percentage of total lipids in the medulla and cortex. Medullary levels of 20∶4n−6 were maintained, 22∶4n−6 declined twice, arachidonic acid was maintained, and 20∶5n−3 was lower. The EFAD diet affected glomerular function, proximal tubular structure and function, and FA distribution in the rat kidney.     

<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).     

Synthesis, characterization and crystal structure of a novel thiocyanate–ruthenium(II) complex

The cis-[Ru(dppb)(Me-bipy)(NCS)₂], dppb = 1,4-bis (diphenylphosphino)butane, Me-bipy = 4,4′-dimethyl-2,2′-bipyridine, and NCS = thiocyanate, was synthesized and characterized by spectroscopic and electrochemical techniques and its structure was determined by crystal X-ray analysis. The crystal structure reveals that the coordination geometry around the Ru(II) center is distorted octahedron where two molecules of thiocyanate are bonded to the ruthenium through nitrogen atom in cis orientation. The half-wave formal potential value E_1/2 = 0.8 V (versus Ag/AgCl) observed is considerable higher than that for the cis-[RuCl₂(dppb)(Me-bipy)] complex, E_1/2 = 0.6 V (versus Ag/AgCl), well illustrating the strong π-acceptor effect the NCS ligand toward the backbonding interaction with the Ru(II) metal center. The MLCT absorption bands of the thiocyanate complex present a higher molar absorptivity (about 12%) compared with the cis-[RuCl₂(dppb)(Me-bipy)] complex, in the same experimental conditions. These properties make the complex potentially promising for the photosensitization process.     

Off-line optimization and control for real time integration of a three-phase hydrogenation catalytic reactor

In order to develop and test the integration procedure, in this paper a real time process integration involving the optimization and control of the process is presented, in this case, with the two-layer approach. The used optimization algorithms were Levenberg–Marquardt and SQP that solve a non-linear least square problem subject to bounds on the variables. The two-layer approach is a hierarchical control structure where an optimization layer calculates the set points and manipulated variables to the advanced controller, which is based on the dynamic matrix control with constraints (QDMC). The non-isothermal dynamic model of the three-phase slurry catalytic reactor with appropriate solution procedure was utilized in this work (Vasco de Toledo, E. C., Santana, P. L., Maciel, M. R. W., & Maciel Filho, R. (2001). Dynamic modeling of a three-phase catalytic slurry reactor. Chemical Engineering Science, 56, 6055–6061). The model consists on mass and heat balance equations for the catalyst particles as well as for the bulk phases of gas and liquid. The model was used to describe the dynamic behavior of hydrogenation reaction of o-cresol to obtain 2-methil-cyclohexanol, in the presence of a catalyst Ni/SiO₂.     

Formation and stability of barium aluminate and cerate in NOx storage-reduction catalysts

The formation and stability of BaAl₂O₄ and BaCeO₃ in Pt-Ba/Al₂O₃ and Pt-Ba/CeO₂ based NO_x storage-reduction (NSR) catalysts has been investigated using kinetic measurements, X-ray diffraction, thermal analysis and X-ray absorption spectroscopy. In as-prepared state, the Ba-component in the NSR catalysts was made up of amorphous BaO and BaCO₃. The formation of BaAl₂O₄ started above 850 °C, whereas the formation of BaCeO₃ was already observed at 800 °C and was faster than that of BaAl₂O₄. The stability of BaAl₂O₄ and BaCeO₃ in various liquid and gaseous atmospheres was different. BaAl₂O₄ was rapidly hydrated at room temperature in the presence of water and transformed to Ba(NO₃)₂ and γ-alumina in the presence of HNO₃, whereas BaCeO₃ was decomposed to much lower extent under these conditions. Interestingly, BaCeO₃ was transformed to Ba(NO₃)₂/CeO₂ in the presence of NO₂/H₂O at 300–500 °C. Also, the presence of CO₂ led to decomposition of barium cerate, which has important consequences for the catalyst ageing under NO_x-storage conditions and can be exploited for regeneration of thermally aged NSR-catalysts.     

Selectivity of Supercritical CO<Subscript>2 </Subscript>in the Fractionation of Hake Liver Oil Ethyl Esters

The solubility of different ethyl esters derivatized from hake liver oil in supercritical carbon dioxide was studied. A selectivity factor was used to determine optimal conditions to fractionate the ethyl ester mixture. A strong influence of solvent pressure and temperature was observed within 8.63–18.04 MPa and 40–70 °C. The lowest total solubility of the ethyl ester mixture was obtained when using supercritical carbon dioxide at the lowest density (the lowest pressure and the highest temperatures value tested). The highest discrimination against long-chain polyunsaturated fatty acids (e.g. EPA and DHA) was also obtained at these above conditions. Conversely, higher solubility and lower selectivity were obtained when solvent density increased. Considering this inverse correlation between selectivity and solubility, a single-step batch-fractionation process was designed to increase the 22:6 ethyl ester content from an initial value of 17.5% in the starting material to 55% in the final extract.     

A voltammetric study concerning the structural stability of Li-overstoichiometric Mg-doped LiCoO2 powders

The effect of Mg-doping and Li overstoichiometry on the structural stability of LiCoO₂ powders has been investigated with emphasis to voltammetric properties. Microparticle cyclic voltammetry (CV) conducted in caustic NaOH to best simulate a non-aqueous electrolyte shows a marked improvement of the structure stability of doped LiCoO₂. In contrast to the unsubstituted LiCoO₂ sample which shows voltammetric peaks associated to the well-known two-phase domain and monoclinic distortion reactions, in Li_1.08Mg_0.06CoO₂, LiMg_0.06CoO₂ and Li_1.08CoO₂ samples these peaks are strongly suppressed providing direct evidence for the existence of a stable solid solution with negligible phase transitions in the reversible intercalation region (3.8-4.2 V vs. Li) as well as in the overcharged region. The effect is higher with Mg-doping, irrespective of the Li overstoichiometry. However, the concomitant presence of Mg and Li excess in the structure is important for obtaining small particle sizes. Since Mg-doping induces a quasi metallic behavior in the samples, whereas the Li excess may provide an higher initial capacity, it is suggested that the Li_1.08Mg_0.06CoO₂ composition may be of interest as positive cathode for advanced Li-ion batteries.     

Effect of different acids with Δ9,12-dienoic structures on Δ9 desaturation activity in rat liver microsomes

The effect of oral administration, for 24 or 48 hr, of different octadeca fatty acids containing a 9,12-dienoic structure on the fatty acid composition and Δ9 desaturation activity of liver microsomes of rat fed a fat-free diet was studied. The ethyl esters of linoelaidic and γ-linolenic acids, the methyl ester of linoleic acid and free columbinic acid were administered to rats maintained on a fat-free diet. The supplementation of the fat-free diet with linoelaidate produced no relevant changes in the fatty acid composition pattern of liver microsomes and did not modify the percentage of conversion of palmitic to palmitoleic acid. The addition of linoleate or γ-linolenate to the fat-free diet returned liver microsome Δ9 desaturation activity toward the control and partially restored the liver microsome fatty acid spectrum found in the fat-free diet. Columbinic acid (5-trans-9-cis,12-cis-18∶3), which cannot be transformed into arachidonic acid, also decreased the Δ9 desaturation activity enhanced by the fat-free diet and evoked changes in the microsomal fatty acid composition similar to those produced by the ω6 fatty acids. These results suggest that the modulation of Δ9 desaturase activity evoked by dietary administration of unsaturated acids of ω6 series would depend on thecis double bond configuration of these acids.     

Observations on the estimation of scavenging activity of phenolic compounds using rapid 1,1-diphenyl-2-picrylhydrazyl (DPPH<Superscript>•</Superscript>) tests

Rapid 1,1-diphenyl-2-picrylhydrazyl (DPPH^•) tests are often applied to classify the scavenging activity of phenolic compounds (AH). Published analytical protocols differ in more than one experimental condition, and results for the relative order or magnitude of activity are often contradictory. In this work, parameters such as duration of test, [AH]/[DPPH^•] molar ratio, and solvent effects were examined and discussed. The test duration and the value of the [AH]/[DPPH^•] ratio did not influence the order of activity among tested antioxidants. Ethanol, commonly used as solvent in such tests, was compared with acetonitrile and tert-butyl alcohol. Solvent properties such as the ability to form hydrogen bonds with the AH seem to influence the level of the relative activity (%RSA). Higher %RSA values were observed in ethanol. The activity of the most polar compounds was affected the most, and in some cases (caffeic, dihydrocaffeic, and rosmarinic acids) the order of activity was changed owing to different kinetics. Standardization of the analytical protocol should include a 20-min reaction period and a molar ratio that permits attainment of a 60–80% RSA value for the most potent antioxidant. Solvent choice is critical for classifying activity. Safe classification can be based only on results from kinetic studies.     

Rheological and morphological properties of high‐density polyethylene and poly(ethylene–octene) blends

The rheological and morphological properties of blends based on high‐density polyethylene (HDPE) and a commercial ethylene–octene copolymer (EOC) produced by metallocene technology were investigated. The rheological properties were evaluated in steady and dynamic shear experiments at 190°C in shear rates ranging from 90 s^?1 to 1500 s^?1 and frequency range between 10^?1 rad/s and 10² rad/s, respectively. These blends presented a high level of homogeneity in the molten state and rheological behavior was generally intermediate to those of the pure components. Scanning electron microscopy (SEM) showed that the blends exhibit dispersed morphologies with EOC domains distributed homogeneously and with particle size inferior to 2 μm. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2240–2246, 2002