Molecular modeling and small angle X-ray scattering studies of Hoplosternum littorale cathodic haemoglobin

Considerable interest is currently focused on fish haemoglobins in order to identify the structural basis for their diversity of functional behavior. Hoplosternum littorale is a catfish that presents bimodal gill (water)/gut (air) -breathing, which allows this species to survive in waters with low oxygen content. The hemolysate of this fish showed the presence of two main haemoglobins, cathodic and anodic. This work describes structural features analyzed here by integration of molecular modeling with small angle X-ray scattering. Here is described a molecular model for the cathodic haemoglobin in the unliganded and liganded states. The models were determined by molecular modeling based on the high-resolution crystal structure of fish haemoglobins. The structural models for both forms of H. littorale haemoglobin were compared to human haemoglobin. (C) 2004 Elsevier B.V. All rights reserved.

Influence of agricultural biomass burning on aerosol size distribution and dry deposition in southeastern Brazil

The size distributed composition of ambient aerosols is used to explore seasonal differences in particle chemistry and to show that dry deposition fluxes of soluble species, including important plant nutrients, increase during periods of biomass (sugar cane trash) burning in São Paulo State, Brazil. Measurements were made at a single site centrally located in the State's sugar cane growing region but away from the immediate vicinity of burns, so that the air sampled was representative of the regional background. Calculation of ion equivalent balances showed that during burning periods smaller particles (Aitken and accumulation modes) were more acidic, containing higher concentrations of SO(4)(2-), oxalate, NO(3)(-), HCOO(-), CH(3)COO(-), and Cl(-), but insufficient NH(4)(+) and K(+) to achieve neutrality. Larger particles showed an anion deficit due to the presence of unmeasured ions and comprised resuspended dusts modified by accumulation of nitrate, chloride, and organic anions. Increases of resuspended particles during the burning season were attributed to release of earlier deposits from the surfaces of burning vegetation as well as increased vehicle movement on unsurfaced roads. During winter months the relative contribution of combined emissions from road transport and industry diminished due to increased emissions from biomass combustion and other activities specifically associated with the harvest period. Positive increments in annual particulate dry deposition fluxes due to higher fluxes during the sugar cane harvest were 44.3% (NH(4)(+)), 42.1 % (K(+)), 31.8% (Mg(2+)), 30.4% (HCOO(-)), 12.8% (Cl(-)), 6.6% (CH(3)COO(-)), 5.2% (Ca(2+)), 3.8% (SO(4)(2-)), and 2.3% (NO(3)(-)). Na(+) and oxalate fluxes were seasonally invariant. Annual aerosol dry deposition fluxes (kg ha(-1)) were 0.5 (Na(+)), 0.25 (NH(4)(+)), 0.39 (K(+)), 0.51 (Mg(2+)), 3.19 (Ca(2+)), 1.34 (Cl(-)), 4.47 (NO(3)(-)), 3.59 (SO(4)(2-)), 0.58 (oxalate), 0.71 (HCOO(-)), and 1.38 (CH(3)COO(-)). Contributions of this mechanism to combined aerosol dry deposition and precipitation scavenging (inorganic species, excluding gaseous dry deposition) were 31% (Na(+)), 8% (NH(4)(+)), 26% (K(+)), 63% (Mg(2+)), 66% (Ca(2+)), 32% (Cl(-)), 33% (NO(3)(-)), and 36% (SO(4)(2-)).

Small-angle X-ray scattering study of gelation and aging of Eu3+-doped sol-gel-derived siloxane-poly(oxyethylene) nanocomposites

The aggregation, gelation, and aging of urea-cross-linked siloxane-poly(oxyethylene) nanohybrids [(U600)-n] containing two different amounts of europium triflate initially dissolved in an ethanol-water mixture were investigated by in situ small-angle X-ray scattering (SAXS). For both low (n = [O]/[Eu] = 80) and high (n = 25) europium contents, the SAXS intensity was attributed to the formation of siloxane clusters of about 8-11 Angstrom in size. Siloxane cluster formation and growth is a rapid process in hybrids with low Eu contents and slow in Eu-rich hybrids. An additional contribution to the scattering intensity at very low angles was attributed to the formation of a coarse structure level. At this secondary level, the structure can be described as a set of dense domains containing siloxane clusters embedded in a depleted matrix composed of unfolded polymer chains and solvent. By fitting a theoretical function for this model to the experimental SAXS curves, relevant structural parameters were determined as functions of time during the sol-gel transition and gel aging. For hybrids with low europium contents (n = 80), the size of the siloxane clusters remains essentially invariant, whereas the dense segregation domains progressively grow. In hybrids with high doping contents (n = 25), the preponderant structure variation during the first stages of the sol-gel transformation is the slow growth of siloxane clusters. For these hybrids, the segregation of siloxane clusters forming dense domains occurs only during advanced stages of the process.

Small angle X-ray scattering study of surface modified tin oxide nanoparticles prepared by sol-gel route

The surface properties of SnO2 nanoparticles were modified by grafting ionic (Tiron (R). (OH)(2)C6H2(SO3Na)(2)(H2O)-H-.) or non-ionic (Catechol (R). C6H4-1,2-(OH)(2)) capping Molecules during aqueous sol-gel processing to improve the redispersibility of powdered xerogel. The effect of the amount of grafted organic molecules on the redispersibility of powders in aqueous solution at several basic pH values was Studied. The nanostructural features of the colloidal suspensions were analyzed by small angle X-ray scattering (SAXS) measurements. Irrespective of the nature and amount of grafted molecules, complete redispersion was obtained in aqueous solution at pH = 13. The redispersion at pH = 11 results in a mixture of dispersed primary particles and aggregates. The proportion of well dispersed nanoparticles and aggregates (and their average size) can be tuned by the quantity of grafted ionic molecules.

Chemical vapor deposition of multi-walled carbon nanotubes from nickel/yttria-stabilized zirconia catalysts

Multi-walled carbon nanotubes (MWNT) were produced by chemical vapor deposition using yttria-stabilized zirconia/nickel (YSZ/Ni) catalysts. The catalysts were obtained by a liquid mixture technique that resulted in fine dispersed nanoparticles of NiO supported in the YSZ matrix. High quality MWNT having smooth walls, few defects, and low amounts of by-products such as amorphous carbon were obtained, even from catalysts with large Ni concentrations (> 50 wt.%). By adjusting the experimental parameters, such as flux of the carbon precursor (ethylene) and Ni concentration, both the MWNT morphology and the process yield could be controlled. The resulting YSZ/Ni/MWNT composites can be interesting due to their mixed ionic-electronic transport properties, which could be useful in electrochemical applications.

Design of a fuzzy Takagi-Sugeno controller to vary the joint knee angle of paraplegic patients

The papers shows, through theoretical studies and simulations, that using the description of the plant by Takagi-Sugeno (T-S), it is possible to design a nonlinear controller to control the position of the leg of a paraplegic patient. The control system was designed to change the angle of the joint knee of 60 degrees. This is the first study that describes the application of Takagi-Sugeno (T-S) models in this kind of problem.

Microstructural and transport properties of LaNiO3-delta films grown on Si(111) by chemical solution deposition

Electrically conductive LaNiO3-delta (LNO) thin films with typical thickness of 200 nm were deposited on Si (111) substrates by a chemical solution deposition method and heat-treated in air at 700 degreesC. Structural, morphological, and electrical properties of the LNO thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), field-emission scanning electron microscopy (FEG-SEM), and electrical resistivity rho(T). The thin films have a very flat surface and no droplet was found on their surfaces. The average grain size observed by AFM and FEG-SEM was approximately 100 nm in excellent agreement with XRD data. The rho(T) data showed that these thin films display a good metallic character in a large range of temperature. These results suggest the use of this conductive layer as electrode in the integration of microelectronic devices. (C) 2003 Elsevier B.V. All rights reserved.

SrBi2Ta2O9 ferroelectric thick films prepared by electrophoretic deposition using aqueous suspension

SrBi2Ta2O9 ferroelectric thick films were prepared by electrophoretic deposition (EPD). For that, ceramic powders were prepared by chemical method in order to obtain compounds with chemical homogeneity. The polymeric precursor method was used for the synthesis of the SrBi2Ta2O9 powder. The crystallographic structure of the powder was examined by X-ray diffraction, and the surface area was determined by single point BET adsorption. The 0.03 vol.% suspension was formed by dispersing the powder in water using two different polymers as dispersants: an ester polyphosphate (C213) and an ammonium polyacrilate (Darvan 821-A). It was investigated the influence of the different dispersants in the surface properties of the powder by zeta potential measurements. The films were deposited on platinum-coated alumina and Pt/Ti/SiO2/Si substrates by a 4 mA constant current, for 10 min, using two parallel electrodes placed at a separation distance of 3 min in the suspension. Several cycles of deposition-drying of the deposit were carried out until reaching the desired thickness. After thermal treatment at temperatures ranging from 700 to 1000 degreesC, the films were characterized by X-ray diffraction and scanning electron microscopy for the microstructure observation. (C) 2003 Elsevier Ltd. All rights reserved.

Electrical characterization of SnO2 : Sb ultrathin films obtained by controlled thickness deposition

A representative study is reported on the electrical properties of SnO2: Sb. ultrathin films (thickness of 40-70 nm) produced by a deposition method based on aqueous colloidal suspensions of 3-5 nm crystalline oxides. The results revealed the films' electrical behavior in a range of 10-300 K, showing a strong dependence on dopant incorporation, with minimum resistivity values in 10 mol % of Sb content. All the samples displayed semiconductor behavior, but the transport mechanism showed a strong dependence on thickness, making it difficult to fit it to well-known models. In thicker films, the mechanism proved to be an intermediary system, with thermally activated and hopping features. Electron hopping was estimated in the range of 0.4-1.9 nm, i.e., in the same order as the particle size. (c) 2007 American Institute of Physics.

Small-angle X-ray scattering and X-ray absorption near-edge structure study of iron-doped siloxane-polyoxyethylene nanocomposites

The local and medium-range structures of siloxane-POE hybrids doped with Fe(III) ions and prepared by the sol-gel process were investigated by X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) and small-angle X-ray scattering (SAXS), respectively. The experimental results show that the structure of these composites depends on the doping level. EXAFS data reveal that, for low doping levels ([O]/[Fe] > 40, oxygens being of the ether-type of the POE chains), Fe(III) ions are surrounded essentially by a shell of chlorine atoms, suggesting the formation of FeCl4- anions. At high doping levels ([O]/[Fe] < 20), Fe(III) ions interacts mainly with oxygen atoms and form FeOx species. The relative proportion of FeOx species increases with iron concentration, this result being consistent with the results of SAXS measurements showing that increasing iron doping induces the formation of iron-rich nanodomains embedded in the polymer matrix.