The sensitization of the ligand-field state of the hexaammineruthenium(II) complex ion by organic compounds

The sensitized photolysis of [Ru(NH3)(6)](2+) by the organic dye rhodamine B and biacetyl was studied under conditions in which only the sensitizer absorbs. The reaction products resulting from ammonia aquation and Ru(II) to Ru(III) oxidation are the same for direct and sensitized photolysis. The energy transfer rate constant, calculated from the fluorescence quenching of rhodamine B, is similar to that estimated from the limiting quantum yield of the photosensitized photoaquation of the complex. Both reactions originate from a common reactive low-lying ligand-field (LF) state, which is also responsible for the direct photolysis reactions. This state, which leads directly to photoaquation, seems to have a certain charge transfer to solvent (CTTS) character, which is responsible for the photo-oxidation products. Sensitization is effective with rhodamine B (17 450 cm(-1)) and biacetyl (19 000 cm(-1)), whereas no reaction is observed with neutral red (16 900 cm(-1)). These results show that the excited state responsible for the photochemical reactions lies in the energy range between 16 900 cm(-1) and 17 700 cm(-1) and possesses spin-orbit character.

Efeitos da amonização sobre a ocorrência de fungos, composição química e digestibilidade in vitro de fenos de grama Seda (Cynodon dactylon (L.) Pers.)

The experiment was conducted with grama seda (Cynodon dactylon (L.) Pers.) hays stored with a low moisture content (12-15%) and without chemical treatment, and hays stored with a high moisture content (20-25%) and treated with anhydrous ammonia (NH3) al 0.5 and 1.0% of DM, and urea at 0.9 and 1.8% of DM. At 65 days after treatment (AT) under a plastic cover, the bales were opened and samples were taken at 3, 15 and 30 days to determine the chemical composition and in vitro digestibility (IVDMD) of the hays. For the identification of fungi, samples were taken at 0, 15 and 30 days AT. The data were analyzed according to a split-plot design with the effects of the chemical treatments studied in the main plot and the effects of the periods of post-treatment studied in the sub-plots, Fourteen genera of fungi were observed in the hays, not treated and treated with NH3 and urea, with a higher occurrence of Cladosporium, Curvularia, Aspergillus, and Penicillium. Treatment with anhydrous ammonia and 1.8% urea controlled the occurrence of Aspergillus; however, Penicillium decreased in hays treated with ammonia 30 days AT. Ammoniation did not influence the contents of ADF, cellulose and lignin in the hays, but NDF and hemicellulose decreased with the use of ammonia 30 days AT. The CP contents and the IVDMD increased with ammoniation. The CP contents decreased in hays treated with NH3 as days AT increase, while hays treated with urea did not change.

Whole-body protein turnover in malnourished patients with child class B and C cirrhosis on diets low to high in protein energy

The purpose of this study was to determine the rate of whole-body protein turnover in moderately and severely alcoholic, malnourished, cirrhotic patients fed with different amounts of protein or energy. Six male patients (Child classes B and C) and four age- and sex-matched healthy control subjects were studied for 18 d in fasting and feeding states; a single oral dose of [N-15]glycine was used as a tracer and urinary ammonia was the end product. The kinetic study showed that patients had higher protein catabolism while fasting (patients: 3.14 +/- 1.2 g of lean body mass/9 h; controls: 1.8 +/- 0.3 g of lean body mass/9 h: P<0.02). Although not statistically significant, protein catabolism (grams of lean body mass/9 h) was lower with the hyperproreic/hyperenergetic diet when compared with fasting. Nitrogen retention was consistent with the lower protein-catabolism rate; a statistically significant increase in nitrogen balance was observed when patients were fed with the hyperproteic/hyperenergetic diet compared with fasting 14.3 +/- 3.2 g of nitrogen/d and -2.2 +/- 1.9 g of nitrogen/d, respectively; P < 0.01). These data indicate that Child class B and C cirrhotic patients are hypercatabolic and that Long-term nutritional intervention with a hyperproteic/hyperenergetic diet is likely needed to improve their clinical and nutritional status. Nutrition 2001;17:239-242. (C) Elsevier B.V. 2001.

Increase on incineration capacity and NOx control for air enrichment in the experimental simulation of aqueous residue incineration

An experimental investigation of air enrichment in a combustion chamber designed to incinerate aqueous residues is presented. Diesel fuel and liquefied petroleum gas (LPG) were used independently as fuels. An increase of 85% in the incineration capacity was obtained with nearly 50% O-2 in the oxidant gas, in comparison to incineration with air only. The incineration capacity continues increasing for enrichment levels above 50% O-2 , although at a lower pace. For complete oxy-flame combustion (100% O-2 ), the increase of the incineration capacity was about 110% relative to the starting conditions and about 13.5% relative to the condition with 50% O-2 . The CO concentration measured near the flame front decreases drastically with the increase of O-2 content in the oxidant gas. At the chamber exit, the CO concentration was always near zero, indicating that the chamber residence time was sufficient to complete fuel oxidation in any test setting. For diesel fuel, the NOx was entirely formed in the first region of the combustion chamber. For diesel fuel, there was some increase in the NOx concentration up to 35% of O-2 ; this increase became very sharp after that. From 60 ppm, at operation with air only, the NOx concentration raises to 200 ppm at 35% O-2 , and then to 2900 ppm at 74% O-2 . The latter corresponds to six times more NOx in terms of the ratio of mass of NO to mass of residue, compared to the situation of combustion with air only. For LPG, the NOx concentrations reached 4200 ppm at 80% O-2 , corresponding to nine times more, also in terms of the ratio of mass of NO to mass of residue, in comparison with combustion with air only. Results of different techniques used to control the NOx emission during air enrichment are discussed: (a) variation of the recirculated zone intensity, (b) increase of the spray Sauter mean diameter, (c) fuel staging, (d) oxidizer staging, and (e) ammonia injection. The present paper shows that NOx emission may be controlled without damage of the increase of incineration capacity by the enrichment and with low emission of partial oxidation pollutants such as CO.

Intestinal starch disappearance increased in steers abomasally infused with starch and protein

Steers (379 +/- 10 kg) with ruminal, duodenal, and ileal cannulas were used in a 5 x 5 Latin square digestion trial to quantify and evaluate the relationship between intestinal protein supply and intestinal starch disappearance. Treatments were infusions of 0, 50, 100, 150, or 200 g/d of casein along with 1,042 g/d of raw cornstarch. Abomasal infusions were accomplished by passing tubing and a pliable retaining washer through the reticular-omasal orifice into the abomasum. Steers were fed a 93% corn silage, 7% supplement diet that contained 12% crude protein at 1.65% body weight in 12 equal portions/d. Periods lasted 17 d (12 d for adaptation, 2 d of collections, and 3 d of rest). The quantity and percentage of organic matter and protein disappearance from the small intestine increased linearly (P < 0.03) with infused casein. Greater quantities of starch disappeared with increased casein infusion (P < 0.01). The infusion of 200 g/d of casein increased small intestinal starch disappearance by 226 g/d over the control. Casein infusion did not affect the quantity or percent of organic matter, starch, or protein disappearance in the large intestine. Treatments did not change ruminal ammonia N, ruminal pH, or plasma glucose concentrations. Starch disappearance from the small intestine was increased with greater protein flow to the duodenum of steers.

Preparation and characterization of spherical silica-porphyrin catalysts obtained by the sol-gel methodology

This work describes the synthesis of a first-generation iron porphyrin catalyst entrapped in a silica matrix by the sol-gel route, leading to spherical particles. The catalyst was synthesized by the method of Stober, through hydrolysis and condensation of the alkoxysilane TEOS in a mixture of alcohol, water and ammonia, in the presence of the iron porphyrin Fe(TPP)Cl. The relation between particle morphology and catalytic activity of the different Fe(TPP)-SiO2, obtained using different H2O/silane molar ratios and ammonia concentrations in the xerogel syntheses, was studied.The obtained catalysts were characterized by UV-vis spectroscopy, NMR Si-29. thermogravimetric analysis and transmission electron microscopy. Their ability to catalyze (Z)-cyclooctene epoxidation and cyclohexane oxidation was tested using iodosylbenzene as oxygen donor; the oxidation products were analyzed by gas chromatography and the catalysts obtained in a form of particles spherical and monodispersed showed to be a promising catalytic system for selective oxidation. (c) 2005 Elsevier B.V. All rights reserved.

Influence of condensed tannins from Brazilian semi-arid legumes on ruminal degradability, microbial colonization and ruminal enzymatic activity in Saanen goats

The present study aimed at determining the influence of condensed tannins present in the Brazilian legume species Mimosa hostilis, Mimosa caesalpinifolia and Bauhinia cheilantha on ruminal degradability, microbial colonization and enzymatic activity. Polyethylene glycol (PEG) was used to reduce the astringency and concentration of soluble condensed tannins. Four ruminally-cannulated Saanen goats (60 +/- 8 kg BW) were fed, in two experimental periods, with a hay diet based on the studied legumes treated or non-treated with PEG. Voluntary intake, microbial colonization, DM, CP, NDF, and ruminal degradability of PEG treated and non-treated forage leaves, as well as pH, ammonia and 1,4 P-endoglucanase activity of the rumen content were evaluated. Astringency and soluble tannin concentration of the studied legumes were reduced by approximately 70% and 50%, respectively, with PEG treatment. Average DM intake was higher for the treated diet (16.76 g DM/kg BW/day against 13.06 g DM/kg BW/day). Percentile values for degradation parameters and for potential and effective degradabilities of DM, CP and NDF were also affected by the tannins, but at different intensities. Electron microscopic observations of ruminally-incubated legume leaves showed a more effective microbial colonization of PEG-treated leaves for all legume species. A decrease in pH and an increase in ammonia concentration and in endoglucanase activity in the ruminal content was also observed for PEG-treated diets at all sampling periods. Condensed tannins of the studied legume species have influenced the adhesion conditions, colonization and enzymatic activity of the microbial ecosystem, and consequently the ruminal degradation of the different dietary fractions. For this reason, the reduction in condensed tannin would be of great importance to improve the nutrition of ruminant feeding of these species. (c) 2005 Elsevier B.V. All rights reserved.

pncA mutations in pyrazinamide-resistant Mycobacterium tuberculosis clinical isolates from the southeast region of Brazil

Objectives: To investigate the presence of mutations in the pncA gene in 31 pyrazinamide-resistant Mycobacterium tuberculosis and 5 susceptible strains. MICs and pyrazinamidase (PZase) activity were also determined.Methods: All 36 M. tuberculosis clinical isolates were genotyped by mycobacterial interspersed repetitive units (MIRUs) and most were also typed by spoligotyping. The MIC value necessary to inhibit 99% of the resistant mycobacterial isolates was determined by microplate Alamar Blue assay (MABA) and by Lowenstein-Jensen assay (LJA). The PZase activity was measured by pyrazinamide deamination to pyrazinoic acid and ammonia, and the entire pncA sequence including the 410 by upstream from the start codon was determined by DNA sequencing of purified PCR products.Results: of the 31 isolates resistant to pyrazinamide, 26 (83.9%) showed at least one mutation in the pncA gene or in its putative regulatory region: Among the 22 different mutations detected in the pncA gene and in its regulatory region, 9 (40.9%) mutations (consisting of six substitutions, two insertions and one deletion) have not been described in previous studies. Three pyrazinamide-resistant isolates, confirmed by MIC varying from 800 to 1600 mg/L, carried the wild-type pncA sequence and retained PZase activity.Conclusions: These results contribute to the knowledge of the molecular mechanism of pyrazinamide resistance in Brazil and also expand the profile of pncA mutations worldwide. The MABA was successfully used to determine the MICs of pyrazinamide.

Chemical Composition and fermentative characteristics of Elephant grass (Pennisetum purpureum Schum.) silages added of increasing levels of mango (Mangifera indica L.) byproducts

Aiming at evaluating the use of those byproducts on ruminant feeding an experiment has been carried out in the Forage Research department (www.npf.ufc.br), in order to evaluate the effects of addition of increasing levels of mango processing byproducts (MB) in Elephant grass silages. Twenty experimental silos made of PVC pipe (100 x 340 mm), in a completely randomized design with 5 levels of addition (0; 5; 10; 15; and 20%) of MB and 4 replications. Upon 32 days of ensilage, samples were collected for determination of levels of dry Matter (DM), crude protein (CP), ethereal extract (EE), neutral detergent fiber (NDF), acid detergent fiber (ADF), hemicelluloses (HC), ammonia nitrogen (N-NH3), and pH values. Data were evaluated by analyses of variance and regression analyses using the F test at the 5% level. The levels of DM and CP increased of 0.50 and 0.03 percentage units, respectively, for every 1% of MB added. The levels of NDF and ADF decreased of 0.51 and 0.24 percentage units, respectively, for every 1% of MB added. The levels of N-NH3 decreased from 4 to 23 percentage units while pH values remained constant (p>0.05), with average values of 3.29. Addition of 20% of MB improved silages chemical composition by promoting an increase in the levels of MS and reduction in the levels of fiber.

Protein-energy status and 15N-glycine kinetic study of child a cirrhotic patients fed low- to high-protein energy diets

In five male cirrhotic patients (Child A) and in four age- and sex-matched healthy control subjects, whole-body protein turnover was measured using a single oral dose of N-15-glycine as a tracer and urinary ammonia as end product. Subjects were studied in the fasting and feeding state, with different levels of protein and energy intake. The patients were underweight and presented lower plasma transthyretin and retinol-binding protein levels. When compared with controls, the kinetic studies showed patients to be hypometabolic in the fasting (Do) state and with the control diet [D-1 = (0.85 g of protein/154 kJ). kg(-1). day(-1)]. However, when corrected by body weight, the kinetic differences between groups disappeared, whereas the N-retention in the feeding state showed better results for the patients due mainly to their efficient breakdown decrease. When fed high-level protein or energy diets [D-2 = (0.9 g protein/195 kJ) and D-3 = (1.56 g protein/158 kJ). kg(-1). day(-1)], the patients showed D-0 = D-1 = D-2 < D-3 for N-flux and (D-0 = D-1) < D-3 (D-2 is intermediary) for protein synthesis. Thus, the present data suggest that the remaining mass of the undernourished mild cirrhotic patients has fairly good protein synthesis activity and also that protein, rather than energy intake, would be the limiting factor for increasing their whole-body protein synthesis.

Valor nutritivo do feno de Brachiaria decumbens Stapf cv. Basilisk submetido a tratamento com amônia anidra ou uréia

The effects of the ammoniation of Brachiaria decumbens hay was evaluated. The hay bales were distributed into a complete randomized block design, with four replications and they were submitted to the treatments: untreated or treated with anhydrous ammonia (NH3)(2,0 and 3,0% of the DM) or with urea (3,6 and 5,4% of the DM). All the hays bales remained under plastic cover for 45 days. After three days of aeration, samples were collected for the determination of the chemical composition, nitrogenous compounds fraction and the in vitro dry matter (IVDDM) and organic matter (IVDOM) digestibility. In the metabolic study, Saanen goats breed was used in a 5x5 Latin squares design, where the apparent digestibility, the voluntary intake and the nutritive value index were evaluated. The ammoniation increased the contents of the total N, N ammonia (N-NH3) and non-protein N, with high effect on the levels of 3,0% of NH3 and 5,4% of urea. There were no differences between the level of 3,0% of NH3 and 5,4% of urea for the total N, N-NH3 and NPN. However, the treatment with 3,0% of NH3 allowed a larger fixation of N in ADIN and NDIN forms. The ammoniation increased the IVDMD and IVDMO and reduced the contents of neutral detergent fiber (NDF), hemicellulose, acid detergent fiber (ADF) and lignin, but it did not alter the cellulose and gross energy contents. The ammoniation increased the DM, OM, CP, NDF, ADF, hemicellulose, cellulose and gross energy apparent digestibility and as well as the voluntary intake of DM, digestible DM, digestible OM, digestible protein, digestible energy and the nutritive value index. The ammoniation increased the hay nutritive value index, but there were no differences between the levels of NH3 and urea.