Study on the lifetime of M-intermediate of bacteriorhodopsin film chemically modified with CeO2 nanoparticles

The characteristics of intermediates of bacteriorhodopsin (bR) can be verified by chemical modification of its surroundings. CeO2 nanoparticles, which were obtained using water-in-oil (W/O) microemulsion and calcined at various temperatures, were used as chemical additive for the modification of bR. X-ray diffraction (XRD) shows that the mean particle sizes for the samples calcined at 500 and 800 degrees C are approximately 10 and 30 nm, respectively. We prepared CeO2 nanoparticle modified poly(vinyl alcohol) (bR-PVA) films with an optical density of about 1.5 at the ground state. It is observed that the lifetime of the Wintermediate for the modified films is prolonged compared with that of the unmodified ones, and the lifetime increases with decreasing particle size. A probable mechanism, which is likely to involve effective molecular interactions between the CeO2 nanoparticles and the bR molecules, is discussed. The hydroxyl groups, which might arise from the interaction between the nanoparticles and the surrounding water molecules, help to lower the ability of the Schiff base of uptaking protons in the Wintermediate. The results indicate that controlling the interactions between biomolecules and various nanomaterials would enlarge the functionality and the range of the application of nanoparticles.

Ionic liquids as solvent and solvent additives for the synthesis of sol-gel materials

The ionic liquid (IL) 1-butyl-3-methylimidazolium chloride was used as a drying control chemical additive in the synthesis of silica sol-gel materials with and without methanol as a co-solvent. The resulting gels were characterized by using thermogravimetric analysis, differential scanning calorimetry, infrared spectroscopy and water sorption kinetics. Calcined gels were analyzed using scanning electron microscopy and nitrogen adsorption isotherms for surface area and pore volume determination. Non-calcined gels were monolithic and showed general cloudiness with lesser degrees observed at higher IL volumes. Calcinations resulted in the formation of powders with increased available surface area as the amount of IL volume was increased. This is consistent with an increase in respective pore volume but a general decrease in average pore size. The resulting materials exhibited conventional structural microdomains, in contrast to periodicity reported when other ionic liquids were used as templates.

Estabilidade aeróbia da ração total e de silagens de capim-marandu tratadas com aditivos químicos e bacterianos

Esta pesquisa foi realizada com o objetivo de determinar o efeito da inclusão de aditivo químico e da inoculação de bactérias homo e heterofermentativas sobre a estabilidade aeróbia de silagens de capim-marandu e da ração total. Foram conduzidos três experimentos para avaliação do benzoato de sódio e de dois inoculantes, um contendo Lactobacillus plantarum + Propionibacterium e o segundo Lactobacillus buchneri. Após 60 dias de fermentação, os silos foram abertos e as silagens e a ração total (RT) contendo silagens de capim-marandu foram colocadas em caixas de isopor e transferidas para câmara climática, a 25 ± 1ºC, para determinação das variações de temperatura na ração total e na silagem, das recuperações de MS e das alterações no pH da silagem. O delineamento experimental foi o inteiramente casualizado, em esquema de parcelas subdivididas. Houve perdas de MS e elevação dos teores de pH quando as silagens foram colocadas em condições de aerobiose. A temperatura das silagens e da RT teve discreto aumento durante os seis dias de aeração. O uso de bactérias ou de benzoato de sódio não influenciou a estabilidade aeróbia das silagens.

Associação entre aditivos químicos e bacterianos na ensilagem de cana-de-açúcar

Objetivou-se avaliar a ensilagem de cana-de-açúcar tratada com três aditivos químicos (uréia 1,5%, benzoato de sódio 0,1% e hidróxido de sódio 1%) mais o grupo controle e duas inoculações (Propionibacterium acidipropionici + Lactobacillus plantarum e Lactobacillus buchneri), em um esquema fatorial 4 x 3 com três repetições para cada tratamento. Avaliou-se o valor nutritivo da forragem antes da ensilagem, após a abertura dos silos e após a exposição aeróbia. As associações de P. acidipropionici ou L. buchneri com NaOH, em comparação ao grupo controle, possibilitaram melhor preservação dos teores de MS (32,2 e 33,5 vs 27,4%, respectivamente), FDN ( 53,4; 55,7 vs 75,3%), FDA (39,5; 44,3 vs 48,7%), lignina (6,6; 7,1 vs 8,1%) e CNF (33,8; 31,7 vs 14,9%) e, conseqüentemente, propiciaram os maiores valores de DIVMS (60,3; 63,2 vs 35,1%). Esses valores podem ser atribuídos ao controle das leveduras pelos efeitos da associação dos aditivos. A ensilagem de cana-de-açúcar requer de forma contundente a inclusão de aditivo.

Perdas de silagens de cana-de-açúcar tratadas com aditivos químicos e bacterianos

Objetivou-se avaliar silagens de cana-de-açúcar tratadas com aditivos químicos (uréia 1,5%; benzoato de sódio 0,1%; ou hidróxido de sódio (NaOH) 1% na matéria natural) combinados ou não com inoculantes (Propionibacterium acidipropionici + Lactobacillus plantarum ou Lactobacillus buchneri). Foram avaliadas 12 silagens: uma controle, sem inoculante e sem aditivo químico; três sem inoculante, mas com um dos aditivos; uma com P. acidipropionici + L. plantarum, sem aditivo químico; três com P. acidipropionici + L. plantarum e um dos aditivos; uma com L. buchneri, sem aditivo químico; e três com L. buchneri e um dos aditivos. Os dados foram analisados em esquema fatorial 4 × 3 com três repetições para cada tratamento. Foram determinadas as perdas ocorridas durante o processo fermentativo nas formas de gases e de efluentes e a recuperação da MS. Durante a exposição aeróbia, determinaram-se a recuperação da MS e a estabilidade aeróbia medida pela variação da temperatura. A associação de L. buchneri e NaOH reduziu as perdas por gases e efluentes e elevou a recuperação da MS. No período após abertura, destacou-se a atuação do benzoato de sódio em manter o pH com variação de apenas 0,1 unidade em cinco dias de exposição aeróbia e dos inoculantes L. buchneri e P. acidipropionici + L. plantarum em prolongar o tempo para elevação da temperatura de 34 horas nas silagens controle para 54 e 50 horas, respectivamente. A ensilagem de cana-de-açúcar requer a inclusão de algum aditivo eficiente no controle das perdas quantitativas durante a fermentação e a exposição aeróbia.

The influence of the mixing time in the rheological behavior of cement pastes

Rheology has the purpose to study the flux and deformation of materials when submitted to some tension or outer mechanical solicitation. In practice, the effective scientific field broached by rheology is restricted only to the study of homogeneous fluids behavior, in which are included eminent liquids, particles suspensions, and emulsions. The viscosity (η) and the yield stress (τ 0) are the two basic values that define the fluids' behavior. The first one is the proportionality constant that relates the shear rate (γ) with the shear stress (τ) applied, while the second indicates the minimal tension for the flowage beginning. The fluids that obey the Newton's relation - Newtonians fluids - display the constant viscosity and the null yield stress. It's the case of diluted suspensions and grate amount of the pure liquids (water, acetone, alcohol, etc.) in which the viscosity is an intrinsic characteristic that depends on temperature and, in a less significant way, pressure. The suspension, titled Cement Paste, is defined as being a mixture of water and cement with, or without, a superplasticizer additive. The cement paste has a non-Newtonian fluid behavior (pseudoplastic), showing a viscosity that varies in accord to the applied shear stress and significant deformations are obtained from a delimited yield stress. In some cases, systems can also manifest the influence of chemical additives used to modify the interactions fluid/particles, besides the introduced modifications by the presence of incorporated air. To the cement paste the rheometric rehearsals were made using the rheometer R/S Brookfield that controls shear stress and shear rate in accord to the rheological model of Herschel-Bulkley that seems to better adapt to this kind of suspension's behavior. This paper shows the results of rheometrical rehearsals on the cement paste that were produced with cements HOLCIM MC-20 RS and CPV-ARI RS with the addition of superplasticizer additives based of napthaline and polycarboxilate, with and without a constant agitation of the mixture. The obtainment of dosages of superplasticizer additives, as well as the water/cement ratio, at the cement at the fluidify rate determination, was done in a total of 12 different mixtures. It's observed that the rheological parameters seem to vary according to the cement type, the superplasticizer type, and the methodology applied at the fluidity rate determination.

Consumo e desempenho de ovinos alimentados com silagens de cana-de-açúcar tratadas com óxido de cálcio e cloreto de sódio

The intake and performance of lambs fed with sugarcane silages treated with whitewash and chloride sodium were evaluated. Seven treatments were used: untreated silage (control); silages treated with 0.5; 1.0 and 1.5% of CaO (whitewash); and silages treated with 0.5; 1.0 and 2.0% of NaCl, with four replicates per treatment. The animals were fed a higher amount of dry matter and total digestible nutrients when the sugarcane silages were treated with 0.5% of NaCl, 1.0 and 1.5% of CaO. The intake of neutral detergent fiber and crude protein increased when the lambs were fed silages treated with 0.5% of NaCl and 1.0% of CaO. The average daily gain did not differ among treatments. The inclusion of 0.5% of sodium chloride and 1.0% of whitewash in sugarcane silages increased the intake and improved the performance of lambs.

High depth-resolution laser ablation chemical analysis of additive-assisted Cu electroplating for microchip architectures

Laser ablation/ionisation mass spectrometry with a vertical resolution at a nanometre scale was applied for the quantitative characterisation of the chemical composition of additive-assisted Cu electroplated deposits used in the microchip industry. The detailed chemical analysis complements information gathered by optical techniques and allows new insights into the metal deposition process.

Species and Hybrids: Chemical and Physical Foliar Attributes and Implications for Herbivory.

Hybridization is an important biological phenomenon that can be used to understand the evolutionary process of speciation of plants and their associated pests and diseases. Interactions between hybrid plants and the herbivores of the parental taxa may be used to elucidate the various cues being used by the pests for host location or other processes. The chemical composition of plants, and their physical foliar attributes, including leaf thickness, trichome density, moisture content and specific leaf weight were compared between allopatric pure and commercial hybrid species of Corymbia, an important subtropical hardwood taxon. The leaf-eating beetle Paropsis atomaria, to which the pure taxa represented host (C. citriodora subsp. variegata) and non-host (C. torelliana) plants, was used to examine patterns of herbivory in relation to these traits. Hybrid physical foliar traits, chemical profiles, and field and laboratory beetle feeding preference, while showing some variability, were generally intermediate to those exhibited by parent taxa, thus suggesting an additive inheritance pattern. The hybrid susceptibility hypothesis was not supported by our field or laboratory studies, and there was no strong relationship between adult preference and larval performance. The most-preferred adult host was the sympatric taxon, although this species supported the lowest larval survival, while the hybrid produced significantly smaller pupae than the pure species. The results are discussed in relation to plant chemistry and physical characteristics. The findings suggest a chemical basis for host selection behavior and indicate that it may be possible to select for resistance to this insect pest in these commercially important hardwood trees.

Molecular Cage Impregnated Palladium Nanoparticles: Efficient, Additive-Free Heterogeneous Catalysts for Cyanation of Aryl Halides

Two shape-persistent covalent cages (CC1(r) and CC2(r)) have been devised from triphenyl amine-based trialdehydes and cyclohexane diamine building blocks utilizing the dynamic imine chemistry followed by imine bond reduction. The cage compounds have been characterized by several spectroscopic techniques which suggest that CC1(r) and CC2(r) are 2+3] and 8+12] self-assembled architectures, respectively. These state-of-the-art molecules have a porous interior and stable aromatic backbone with multiple palladium binding sites to engineer the controlled synthesis and stabilization of ultrafine palladium nanoparticles (PdNPs). As-synthesized cage-embedded PdNPs have been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and powder X-ray diffraction (PXRD). Inductively coupled plasma optical emission spectrometry reveals that Pd@CC1(r) and Pd@CC2(r) have 40 and 25 wt% palladium loading, respectively. On the basis of TEM analysis, it has been estimated that as small as similar to 1.8 nm PdNPs could be stabilized inside the CC1(r), while larger CC2(r) could stabilize similar to 3.7 nm NPs. In contrast, reduction of palladium salts in the absence of the cages form structure less agglomerates. The well-dispersed cage-embedded NPs exhibit efficient catalytic performance in the cyanation of aryl halides under heterogeneous, additive-free condition. Moreover, these materials have excellent stability and recyclability without any agglomeration of PdNPs after several cycles.

Low-temperature growth of cubic GaN by metalorganic chemical-vapor deposition

Low-temperature growth of cubic GaN at 520 degrees C was achieved using CCl4 as an additive by metalorganic chemical-vapor deposition (MOCVD) on GaAs substrate. X-Ray measurement confirmed that the films are single-phase cubic GaN. Scanning electron microscopy (SEM) and reflection high-energy electron diffraction (RHEED) were also used to analyze the surface morphology and the quality of films. The evolution of surface morphology suggests that CCl4 can reduce the hopping barrier and thus Ga adatoms are able to diffuse easily on the GaN surface. (C) 1998 Elsevier Science S.A. All rights reserved.

Using an additive to control the electrospinning of fibres of poly(epsilon-caprolactone)

Electrospinning is a route to polymer fibres with diameters considerably smaller than available from most fibre-producing techniques. We explore the use of a low molecular weight compound as an effective control additive during the electrospinning of poly(epsilon-caprolactone). This approach extends the control variables for the electrospinning of nanoscale fibres from the more usual ones such as the polymer molecular weight, solvent and concentration. We show that through the use of dual solvent systems, we can alter the impact of the additive on the electrospinning process so that finer as well as thicker fibres can be prepared under otherwise identical conditions. As well as the size of the fibres and the number of beads, the use of the additive allows us to alter the level of crystallinity as well as the level of preferred orientation of the poly(epsilon-caprolactone) crystals. This approach, involving the use of a dual solvent and a low molar mass compound, offers considerable potential for application to other polymer systems. (C) 2010 Society of Chemical Industry

Effects of high hydrostatic pressure and chemical reduction on the emulsification properties of gum arabic

Gum arabic is widely used in the food industry as an additive, both as a thickener and an emulsifier. This study has compared the emulsification properties of two types of gums, KLTA (Acacia senegal) and GCA (Acacia seyal), both in their native/untreated forms and after exposure to high pressure (800 MPa). Further studies were undertaken to chemically modify the disulphide linkages present and to investigate the effects of their reduction on the diffusion of the carbohydrate materials. The emulsification properties of the gum samples were examined by determining the droplet size distribution in a ‘‘model’’ oil-in-water system. Results showed that high pressure treatment and chemical reduction of gums changed the emulsification properties of both gums. The high molecular weight component in arabinogalactanproteins (AGP/GP), and more ‘‘branched’’ carbohydrates present in gum arabic, may be responsible for the emulsification properties of GCA gum, indicating that the emulsification mechanisms for KLTA and GCA were different.

Chemical process to separate iron oxides particles in pottery sample for EPR dating

Ancient potteries usually are made of the local clay material, which contains relatively high concentration of iron. The powdered samples are usually quite black, due to magnetite, and, although they can be used for thermoluminescene (TL) dating, it is easiest to obtain better TL reading when clearest natural or pre-treated sample is used. For electron paramagnetic resonance (EPR) measurements, the huge signal due to iron spin-spin interaction, promotes an intense interference overlapping any other signal in this range. Sample dating is obtained by dividing the radiation dose, determined by the concentration of paramagnetic species generated by irradiation, by the natural dose so as a consequence, EPR dating cannot be used, since iron signal do not depend on radiation dose. In some cases, the density separation method using hydrated solution of sodium polytungstate [Na(G)(H(2)W(12)O(40))center dot H(2)O] becomes useful. However, the sodium polytungstate is very expensive in Brazil: hence an alternative method for eliminating this interference is proposed. A chemical process to eliminate about 90% of magnetite was developed. A sample of powdered ancient pottery was treated in a mixture (3:1:1) of HCI, HNO(3) and H(2)O(2) for 4 h. After that, it was washed several times in distilled water to remove all acid matrixes. The original black sample becomes somewhat clearer. The resulting material was analyzed by plasma mass spectrometry (ICP-MS), with the result that the iron content is reduced by a factor of about 9. In EPR measurements a non-treated natural ceramic sample shows a broad spin-spin interaction signal, the chemically treated sample presents a narrow signal in g= 2.00 region, possibly due to a radical of (SiO(3))(3-), mixed with signal of remaining iron [M. lkeya, New Applications of Electron Spin Resonance, World Scientific, Singapore, 1993, p. 285]. This signal increases in intensity under -gamma-irradiation. However, still due to iron influence, the additive method yielded too old age-value. Since annealing at 300 degrees C, Toyoda and Ikeya IS. Toyoda, M. Ikeya, Geochem. J. 25 (1991) 427-445] states that E `(1)-signal with maximum intensity is obtained, while annealing at 400 degrees C E`(1)-signal is completely eliminated, the subtraction of the second one from 300 degrees C heat-treated sample isolate E`(1)-like signal. Since this is radiation dose-dependent, we show that now EPR dating becomes possible. (C) 2008 Elsevier B.V. All rights reserved.