Photoinduced phenomena in layer-by-layer films of poly(allylamine hydrochloride) and Brilliant Yellow azodye

The nanoscale interactions between adjacent layers of layer-by-layer (LBL) films from poly(allylamine hydrochloride) (PAH) and azodye Brilliant Yellow (BY) have been investigated, with the films employed for optical storage and the formation of surface-relief gratings. Using Fourier transform infrared spectroscopy, we identified interactions involving SO3- groups from BY and NH3+ groups from PAH. These electrostatic interactions were responsible for the slow kinetics of writing in the optical storage experiments, due to a tendency to hinder photoisomerization and the subsequent reorientation of the azochromophores. The photoinduced birefringence did not saturate after one hour of exposure to the writing laser, whereas in azopolymer films, saturation is normally reached within a few minutes. on the other hand, the presence of such interactions prevented thermal relaxation of the chromophores after the writing laser was switched off, leading to a very stable written pattern. Moreover, the nanoscale interactions promoted mass transport for photoinscription of surface-relief gratings on PAH/BY LBL films, with the azochromophores being able to drag the inert PAH chains when undergoing the trans-cis-trans photoisomerization cycles. A low level of chromophore degradation was involved in the SRG photoinscription, which was confirmed with micro-Raman and fluorescence spectroscopies.

Preservação do Feno de Brachiaria decumbens Stapf cv. Basilisk Submetido a Tratamento com Amônia Anidra ou Uréia

This study was conducted to evaluate the effects of anhydrous ammonia (NH3) or urea treatment on the occurrence of fungi in hays of Brachiaria decumbens Stapf cv. Basilisk, baled and stored with different moisture contents. The following treatments were evaluated: T-1 = green forage, soon after the harvest; T-2 = hay with 25% of moisture, with evaluation before baling; T-3 = hay with 13% of moisture and untreated; T-4 = hay with 25% of moisture + .5% of NH3 in the DM T-5 = hay with 25% of moisture +1% of NH3 in the DM; T-6 = hay with 25% of moisture +.9% of urea in the DM and T-7 = hay With 25% of moisture +1.8% of urea in the DM. The treated hays stayed under plastic cover during 75 days, and samples were collected soon after the opening of the bales piles,and they were immediately analyzed in the laboratory. Eleven fungi were identified in different treatments, with high incidence of Aspergillus in the untreated hay, in the hay stored with 25% of moisture and treated with .5% NH3. The ammoniation totally reduced the occurrence of Helminthosporium and Nigrospora, but it did not control the occurrence of Cladosposrium and caused the occurrence of Penicillium in large intensity. The occurrence of Epicoccum, Curvularia, Phitomyces and Aspergillus genus were totally controlled by the treatment of hay with 1% of NH3; .9 and 1.8% of urea.

Tuning the acidic properties of aluminas via sol-gel synthesis: New findings on the active site of alumina-catalyzed epoxidation with hydrogen peroxide

This study answers several pending questions about alumina-catalyzed epoxidation with aqueous 70 wt% H2O2. To evaluate the effect of the water-to-aluminum tri-sec-butoxide molar ratio, this was systematically changed from 1 to 24. The xerogels were calcined at 450 degrees C and gave different gamma-Al2O3's with distinct textural and acidic properties. A combination of Al-27 MAS NMR and TPD-NH3 results of calcined aluminas allowed us to assign the type la. Al-OH sites as the catalytic sites for epoxidation. The type Ib Al-OH sites have no function in catalytic epoxidation, because ethyl acetate poisons these sites. The strong acid sites of types IIa, IIb, and III Al-OH groups are responsible for the undesired H2O2 decomposition and decreased oxidant selectivity. (c) 2006 Elsevier B.V. All rights reserved.

Efeitos da amonização sobre o valor nutritivo do feno de capim-braquiária

This work was conducted to determine the effects of ammoniation and supplementation on the nutritive value of signal grass (Brachiaria decumbens Stapf) hay. The hay was treated with anhydrous ammonia (3.0% DM) and introduced into the rations for sheep with 12.00% of CP, identified as T1 grass hay without NH3 + cotton seed meal; T2 = treated hay (3.0% de NH3); T3 = treated hay (3.0% de NH3) + com grain meal; T4 = hay + cotton seed meal + corn grain meal. nit: following coefficients of digestibility were determined for T1, T2, T3 e T4, respectively: DM (54.90; 55.50); 54.50; and 56.12%); NI)I: (51.36; 60.20; 55.30; and 48.35%); ADF (47.36; 58.66; 56.03; and 47.07%); hemicellulose (58.80; 63.32; 56.00; and 49.70%); cellulose (55.58; 71.80; 68.07; and 58.21%); lignin (10.10; 32.18; 31.74; and 0.72%) and protein (64.6; 59.36; 56.16; and 70. 15%). nle N balances for T1, T2, T3 and T4 were 5.69; 3.88; 3.90; and 8,82 g N/day. It was concluded that the ammoniation was equivalent to the vegetable protein supplementation in the rations. Furthermore, this treatment showed a greater potential to increase fiber digestion, particulary for ADF and cellulose.

Effect of ammoniation and moisture-content on the quality of signal grass (Brachiaria-decumbens stapf) hay

The experiment was carried out to evaluate the effects of two moisture levels (18-20% and 13-15%) and three anhydrous ammonia levels (0.0; 1.5; 3.0% of NH3) on the quality of Brachiaria decumbens Stapf hay. The hay was bailed in April and weighed and treated under plastic cover during 30 days. The hay presented a similar chemical composition when bailed with high or low moisture. The percentages of NDF (80.59; 77.61; 76.10%); hemicellulose (32.56; 29.48; 28.76%) and lignin (9.53; 8.21; 7.54% decreased and the percentages of crude protein (4.04; 11.35; 13.22%) and IVDMD (36.78; 49.72; 54.33%) increased as the NH3 level increased. The fractions ADF, cellulose, and ADIN did not change due to the ammoniation. The incidence of fungi decreased with application of NH3 being the better results obtained with the 1.5% treatments.

REDUCTION OF THE AMIDO-BONDED (2-PICOLINAMIDO)PENTAAMMINERUTHENIUM(III) FOLLOWED BY FORMATION OF CIS-(2-PICOLINAMIDE)TETRAAMMINERUTHENIUM(II)

[(NH3)(5)Ru-III(2-NCpy)], obtained from electrochemical oxidation of the Ru(II) complex, undergoes hydrolysis to the amido-bonded [Ru-III(NHC(O)-2-py)]. The electrochemical reduction of this latter complex to Ru(II) is followed by an aquation reaction to form [R(II)(NH3)(5)(OH2)] and free picolinamide and a chelation reaction to form cis-[R(II)-(NH3)(4)(2-pica)] with the displacement of one cis ammonia.

Spherical particles of phenolic resin treated with iron oxide

This paper describes the preparation and characterization of phenolic resins' thermospheres covered by a magnetic phase of iron oxide. The thermospheres were prepared by allowing phenol and formaldehyde to react under dispersion polymerization conditions and the iron oxide phase was incorporated in situ onto the phenolic resin particles by adding concentrated NH3 to FeCl2 in DMSO. This reaction was conducted at 70 degrees C under nitrogen atmosphere in a controlled temperature vessel, and the modified resin was isolated and dried in vacuo. Both pure and modified resins were characterized by DRX, TG- DTA, and MEV/ EDX. The modified particles were attracted by a magnetic field, indicating the fixation of magnetic iron oxide. No diffraction peaks were observed in DRX analysis; thermal analysis ( DTA) of both pure and modified resins presented exothermic events between 300 and 680 degrees C, and 300 and 570 degrees C, respectively, indicating the microstructure of the resin was modified after the treatment. Thermogravimetric analysis ( TGA) of the pure resin registered a 2.0% residue, compared to 8.0% for the modified resin. These residues correspond to about 7.0% of fixed iron oxide. MEV/ EDX analyses confirm the modification of the resins by the process of fixing iron oxide.

Atmospheric emission of reactive nitrogen during biofuel ethanol production

This paper evaluates emissions to the atmosphere of biologically available nitrogen compounds in a region characterized by intensive sugar cane biofuel ethanol production. Large emissions of NH(3) and NO,, as well as particulate nitrate and ammonium, occur at the harvest when the crop is burned, with the amount of nitrogen released equivalent to similar to 35% of annual fertilizer-N application. Nitrogen oxides concentrations show a positive association with fire frequency, indicating that biomass burning is a major emission source, with mean concentrations of NO, doubling in the dry season relative to the wet season. During the dry season biomass burning is a source of NH3, with other sources (wastes, soil, biogenic) predominant during the wet season. Estimated NO(2)-N, NH(3)-N, NO(3)(-)-N and NH(4)(+)-N emission fluxes from sugar cane burning in a planted area,of ca. 2.2 x 10(6) ha are 11.0, 1.1, 0.2, and 1.2 Gg N yr(-1), respectively.

Metal carbonyls with zinciron bond: synthesis and vibrational spectra

The compounds of the type LZnFe(CO)4 (L = dien, trien, tn, s-diMeen, Meen) not yet reported and (NH3)3ZnFe(CO)4, already known, were prepared and studied by IR and Raman spectroscopy. The data obtained suggest that LZnFe(CO)4, for L = (NH3)3, dien and trien are monomers with a bipyramidal trigonal configuration around the iron atom, while for L = tn, s-diMeen and Meen the complexes are probably polymers having a center of symmetry with iron atoms octahedrally co-ordinated. © 1979.

Kinetic studies on the reactions of Ru(II) tetraammines with CS2N- 3

The kinetics of the reactions of Ru(II) complexes with CS2N- 3 ions were studied spectrophotometrically. The formation rate constants data for trans-[Ru(NH3)4L(CS2N3)] are 2.2 × 102, 1.8 × 10 and 1.3 × 102 M-1 s-1 for L = SO2- 3, HSO- 3 and P(OEt)3), respectively [μ = 1.0 M (NaCF3COO), 25°C]. Under the same experimental conditions, the values of k-1 (specific rate for the aquation reaction) are 1.5 × 10-2, 5.0 × 10-2 and 4.5 × 10 s-1 for L = SO2- 3, HSO- 3 and P(OEt)3, respectively. The free-energy change (ΔG≠) for the systems where L = P(OEt)3 and SO2- 3 are in agreement within the experimental error. It was observed that the affinity of the CS2N- 3 ion decreases with the increasing π-acidity of the auxiliary ligand L. The order of affinity of the CS2N- 3 ion for the Ru(II) center studies is SO2- 3 > HSO- 3 > P(OEt)3 >SO2. © 1986.

Synthesis and characterization of ruthenium complexes immobilized on poly(4-vinylpyridine)

The [Ru(NH3)5(H2O)]2+ and trans-[Ru(NH3)4SO2(H2O)]2+ complexes ions were immobilized on poly(4-vinylpyridine) (4-PVP) through reactions in aqueous solutions. The stability of the imobilized complexes was checked in aqueous solution in the pH 2.0-8.0 range. The number of pyridinic nitrogens in the polymer 4-PVP is 2.80±0.05 mmol/g according to nitrogen elemental analysis. Potentiometric titration experiments showed that the accessible nitrogen, in aqueous medium, was 0.94±0.02 mmol/g with a p Ka value of 7.4±0.2. In addition, ruthenium and sulfate analysis has demonstrated that about 15% of the accessible nitrogen sites are able to coordinate to the metal centers. The characterization of the immobilized complexes was made through diffuse electronic and infrared spectroscopies and differential pulse and cyclic voltammetries. © 1993 Plenum Publishing Corporation.

Avaliação do triticale (X triticosecale wittimack) para silagem

Silages from three cultivars of triticale (X Triticosecale wittimack) were evaluated at the UNESP, Jaboticabal, Brazil. The cultivars FCA VJ-CB-01, FCA VJ-CB-02, and FCA VJ-CB-03 were harvested for silage in three growing stages of maturity; beginning of flowering, (S1), milk stage (S2), and dough stages (S3). Data were analyzed by randomized complete block with three replications. The DM (%) values increased while the CP (%DM) and buffering capacity (me HCl/100 g DM) decreased with plant development. Silages of plants harvested at S3 stage had higher pH and N-NH3 values compared to the S1 and S2 silages. The soluble carbohydrates contents (%DM) were higher at the S2 stage (16.9%) and were not different at the S1 (8.7%) and S3 (9.2%) stages. The crude energy contents (Kcal/kg MS) increased while the ADF, NDF, cellulose, and hemicellulose (DM%) decreased due to the presence of dough grains. This was not observed with the lignin contents. The IVDMD values were 66.3, 60.1 and 58.9%, for plants harvested at the S1, S2, and S3 stages, respectively. The results showed that there was no difference among for chemical composition, crude energy, and for IVDMD.

Estádio de desenvolvimento do milho. 3. Avaliação de silagens por intermédio de parâmetros de fermentação ruminal

The objective of this experiment was to analyze the rumen fermentation of silages made from corn harvested at milk stage (MS), milk early dough stage (MEDS), medium dough stage (MDS) and semi-hard dough stage (SHDS). Rumen fluid was collected from sheep by esophageal tube at 0, 1, 3 and 6 hours after feeding. There were no differences among silages for ammonia nitrogen (NH3-N) and methylene blue reduction time (MBRT). Only the MS and SHDS silages differed in rumen pH (6.82 and 6.53, respectively). Differences in total rumen VFA and acetic acid concentrations (mmoles/L) were observed among stages, but not between MS (36.40 and 22.13) and MEDS (42.49 and 25.73), nor between MDS (64.52 and 40.34 respectively) and SHDS (64.09 and 43.61, respectively). The periods of 1 and 3 hours after feeding showed the smallest pH values (6.47 and 6.63), the highest NH3-N concentrations (9.75 and 10.56 mg/dL) and the highest concentrations of total VFA, and acetic and propionic acids (60.33, 37.05 and 16.73; 59.40, 35.28 and 16.84 mmoles/L, respectively). On the whole, the MDS and SHDS silages showed the best rumen fermentation patterns based on pH and total and individual VFA values.

Diferentes níveis de torta de nabo forrageiro (Raphanus sativus) como aditivo na silagem de capim elefante

The aim of the study was to evaluate the effects of the inclusion of different levels of turnip cake (TNF) on the chemical composition, digestibility and quality of elephant grass silage. Due to the quality of the oil extracted from the seeds, the turnip is being considered as an important option for the biodiesel industry in Brazil. The turnip cake is obtained from the mechanical pressing of the seeds to produce oil, and it differs from the meal by the content of fat. In the meal the fat is less than 1%, due to the use of solvents for the oil extraction. Experimental silos were used in a completely randomized design, in factorial arrangement 2 x 3 (two types of material and four levels of inclusion). The materials were represented for original material (fresh) and ensiled material, with four levels of inclusion of TNF (0, 3, 6, and 9%). Dry matter (DM), ether extract (EE), crude protein (CP), neutral detergent fiber (NDF), acid detergent fiber (ADF), nitrogen indigestible neutral detergent (NIDN), nitrogen indigestible acid detergent (NIDA), ash (MM), lignin (LIG), buffer power (PT), calcium (Ca), phosphorus (P) and in vitro dry matter digestibility (IVDDM) were determined in all materials. In silage, additionally, were determined pH and amoniacal nitrogen (NH3-N). There were effects of inclusion of TNF and the type of material on the DM, CP, ADF, NIDA, P, and MM contents and on IVDDM. The interaction of the two factors was observed to the contents of CP, NDF, ADF, NIDA, Ca and IVDDM. In silage, the DM levels were lower (P < 0.05) than in original material. The values of DM were increased linearly as increased levels of inclusion of TNF. The fibrous components, including NIDN and NIDA, decreased linearly when the TNF increased. In all treatments, values of pH and N-NH3 considered ideal for good silage were observed. The IVDDM was reduced, linearly, with the addition of increasing levels of TNF. A negative correlation (-0.95) between IVDDM and content of EE may explain the tendency of this variable, due to the EE content increased linearly with the addition of TNF. The addition of TNF as an additive in silage of elephant diminished IVDDM. Considering the changes observed in the chemical composition and digestibility of elephant grass silage with TNF as additive, suggests that this should not be included at levels exceeding 3%. On the other hand, the silages with TNF as additive showed appropriate fermentation characteristics.

Analysis of agonist and antagonist effects on thyroid hormone receptor conformation by hydrogen/deuterium exchange

Thyroid hormone receptors (TRs) are ligand-gated transcription factors with critical roles in development and metabolism. Although x-ray structures of TR ligand-binding domains (LBDs) with agonists are available, comparable structures without ligand (apo-TR) or with antagonists are not. It remains important to understand apo-LBD conformation and the way that it rearranges with ligands to develop better TR pharmaceuticals. In this study, we conducted hydrogen/deuterium exchange on TR LBDs with or without agonist (T 3) or antagonist (NH3). Both ligands reduce deuterium incorporation into LBD amide hydrogens, implying tighter overall folding of the domain. As predicted, mass spectroscopic analysis of individual proteolytic peptides after hydrogen/ deuterium exchange reveals that ligand increases the degree of solvent protection of regions close to the buried ligand-binding pocket. However, there is also extensive ligand protection of other regions, including the dimer surface at H10-H11, providing evidence for allosteric communication between the ligand-binding pocket and distant interaction surfaces. Surprisingly, Cterminal activation helix H12, which is known to alter position with ligand, remains relatively protected from solvent in all conditions suggesting that it is packed against the LBD irrespective of the presence or type of ligand. T 3, but not NH3, increases accessibility of the upper part of H3-H5 to solvent, and we propose that TR H12 interacts with this region in apo-TR and that this interaction is blocked by T 3 but not NH3.Wepresent data from site-directed mutagenesis experiments and molecular dynamics simulations that lend support to this structural model of apo-TR and its ligand-dependent conformational changes. (Molecular Endocrinology 25: 15-31, 2011). Copyright © 2011 by The Endocrine Society.