Showing papers by "Federal University of São Carlos published in 2001"

Cyclohexane oxidation continues to be a challenge

Abstract: Many efforts have been made to develop new catalysts to oxidize cyclohexane under mild conditions. Herein, we review the most interesting systems for this process with different oxidants such as hydrogen peroxide, tert -butyl hydroperoxide and molecular oxygen. Using H 2 O 2 , Na-GeX has been shown to be a most stable and active catalyst. Mesoporous TS-1 and Ti-MCM-41 are also stable, but the use of other metals such as Cr, V, Fe and Mo leads to leaching of the metal. Homogeneous systems based on binuclear manganese(IV) complexes have also been shown to be interesting. When t -BuOOH is used, the active systems are those phthalocyanines based on Ru, Co and Cu and polyoxometalates of dinuclear ruthenium and palladium. Microporous metallosilicates containing different transition metals showed leaching of the metal during the reactions. Molecular oxygen can be used directly as an oxidant and decreases the leaching of active species in comparison to hydrogen peroxide and tert -butyl hydroperoxide. Metal aluminophosphates (metal: Mn, Fe, Co, Cu, Cr V) are active and relatively stable under such conditions. Mn-AlPO-36 yields directly adipic acid, but large amounts of carboxylic acids should be avoided, as they cause metal leaching from the catalysts. Rare earth exchanged zeolite Y also shows good selectivity and activity. In the last part of the review, novel alternative strategies for the production of cyclohexanol and cyclohexanone and the direct synthesis of adipic acid are discussed.

Highly bioactive P2O5–Na2O–CaO–SiO2 glass-ceramics

Abstract: Glasses having a chemical composition between 1Na2O–2CaO–3SiO2 (1N2C3S) and 1.5Na2O–1.5CaO–3SiO2, containing 0, 2, 4 and 6 wt% P2O5, were crystallized to several volume percent through thermal treatments in the range 550–700 °C. These glasses and glass-ceramics were exposed to a simulated body fluid solution (SBF-K9 which is close to human plasma) for several time periods. Fourier transform infrared spectroscopy (FTIR) was used to determine the rate of hydroxy carbonate apatite (HCA) formation. Crystallization decreased the kinetics but did not inhibit the development of a HCA layer, even in fully crystallized ceramics. The onset time for crystallization of HCA varied from 8 h for a glass containing 6% P2O5 to 35 h for a fully crystallized 1.07Na2O–2CaO–3SiO2 ceramic. The HCA layer formation of these compositions in `in vitro' tests is much faster than in commercial bioactive materials such as synthetic hydroxyapatite ceramic, A/W glass-ceramic, Ceravital and Bioverit, for which the onset time usually takes at least seven days. FTIR and inductive coupled plasma studies confirmed the formation of an apatite layer which indicates bioactivity in the 1N2C3S crystal phase. X-ray diffraction experiments show that the phosphorus ions are kept in solid solution in the crystal phase. An apatite-like compound only appeared when the specimens were submitted to very long additional thermal treatments. The bioactivity of commercial materials is based on the apatite crystal phase, while the high level of bioactivity of this new generation of glass-ceramics is attained due to the combination of two mechanisms acting simultaneously; a non-phosphate bioactive crystal phase (1N2C3S) and the phosphorus ions in solid solution which are easily released from the structure, promoting a faster HCA layer formation similar to 45S5 Bioglass®.

Activity and Characterization by XPS, HR-TEM, Raman Spectroscopy, and BET Surface Area of CuO/CeO2-TiO2 Catalysts

Abstract: Structural and textural studies of a CuO/TiO2 system modified by cerium oxide were conducted using Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and N2 absorption (BET specific surface area). The introduction of a minor amount of CeO2 (Ce0.09Ti0.82O1.91Cu0.09 sample) resulted in a material with the maximum surface area value. The results of Raman spectroscopy revealed the presence of only two crystalline phases, TiO2 anatase and CeO2 cerianite, with well-dispersed copper species. TEM micrographs showed a trend toward smaller TiO2 crystallites when the cerium oxide content was increased. The XPS analysis indicated the rise of a second peak in Ti 2p spectra with the increasing amount of CeO2 located at higher binding energies than that due to the Ti4+ in a tetragonal symmetry. The CuO/TiO2 system modified by CeO2 displayed a superior performance for methanol dehydrogenation than the copper catalyst supported only on TiO2 or CeO2.

Two 5S rDNA arrays in neotropical fish species: is it a general rule for fishes?

Abstract: In this paper we describe Southern blot hybridization results probed with 5S rRNA genes for several Neotropical fish species representing different taxonomic groups. All the studied species showed a general trend with the 5S rDNA tandem repeats organized in two distinct size-classes. At the same time, data on 5S rDNA organization in fish genome were summarized. Previous information on the organization and evolution of 5S rRNA gene arrays in the genome of this vertebrate group are in agreement with the Southern results here presented. Sequences obtained for several fish species have revealed the occurrence of two distinct 5S rDNA classes characterized by distinct nontranscribed spacer sequences, which are clustered in different chromosomes in some species. Moreover, the 5S rDNA loci are generally distributed in an interstitial position in the chromosomes and they are usually not syntenic to the 45S rDNA. The presence of two classes of 5S rDNA in several non-related fish species suggests that this could be a common condition for the 5S rRNA gene organization in the fish genome.

Mixing and turbulent fluxes in the metalimnion of a stratified lake

Abstract: Turbulent mixing within the metalimnion of a stratified lake was investigated using a portable flux profiler (PFP) capable of resolving all three components of the velocities, the conductivity, and the temperature microstructure. Presented is a detailed description of the techniques used in the data processing, particularly in the separation of the turbulence from the internal wave signal. The sampling, carried out in Lake Kinneret (Israel) during the summer for 3 consecutive years, showed that most of the time the vertical flux through the metalimnion was negligible, but, at times, the eddy diffusivity did reach values as high as 10 22 m 2 s 21 . A comparison between direct measurement of the vertical fluxes obtained from the PFP data with that from indirect estimates of the fluxes shows good agreement for the 6 # Frg , 100 range. Scaling of the turbulence based on Frg and Ri reveal two classes of turbulent regimes: (1) due to traumata characteristic of internal wave‐wave interaction and, another, (2) more energetic and due to shear-driven turbulence. The PFP penetrated the water relatively slowly (0.1 m s 21 ) allowing the measurement of temperature fluctuations down to 1 mm and, at the same time, also providing information of the velocity fluctuations. This is different from previous oceanographic measurements, which are always gathered with instrument traversing the water column at velocities closer t o1ms 21 , preventing regime (1) from being detected.

The effect of therapeutic ultrasound on repair of the achilles tendon (tendo calcaneus) of the rat

Abstract: The purpose of this study was to evaluate the effects of therapeutic ultrasound (US) on the healing process in the Achilles tendon (Tendo calcaneus) of Wistar rats after tenotomy. Sonication was performed at a frequency of 1 MHz, an intensity of 0.5 W/cm(2) (SATA), for 5 min, over a period of 14 consecutive days in two modalities (n = 15); in both continuous and pulsed modes. The control group was divided into tenotomized, mock-sonicated and nontenotomized tendons (n = 15). On the 15th postoperative day, the tendons were removed and analyzed by using the polarized light microscopy, with the purpose of detecting and measuring the organization of collagen fibers through birefringence. The results showed a high birefringence for the tendons treated using the pulsed mode (p < 0.001), revealing the best organization and aggregation of collagen bundles. Sonication in the continuous mode induced a decrease (p = 0.047) in the ability to quicken the healing process. These findings suggest that US therapy is beneficial in the early healing process of tendons when the pulsed mode is used.

Dose-dependency of low-energy HeNe laser effect in regeneration of skeletal muscle in mice.

Abstract: . We evaluated the effect on mice skeletal muscle regeneration of different doses (2.6, 8.4, and 25 J/cm2) of HeNe laser (λ 632.8 nm; power, 2.6 mW; spot size, 0.007 cm2) applied directly to intact skin of injured muscle. Muscle injury was induced in both right and left Tibialis anterior (TA) muscles by ACL myotoxin (5 mg/kg). Right TA muscles were irradiated daily for 5 days while contralateral muscles received a sham treatment. Only the 2.6 J/cm2 dose resulted in changes such as increased mitochondrial density and muscle fibre in the TA muscles as compared to sham groups (3280±704 µm2 versus 2110±657 µm2, p=0.02). We concluded that the HeNe effect on mouse muscle regeneration is dose-specific: only 2.6 J/cm2 increased muscle fibre area and mitochondrial density.

Nonstationary Casimir effect and analytical solutions for quantum fields in cavities with moving boundaries

Abstract: This is a review of publications on classical and quantum electrodynamics in cavities with moving boundaries (in the quantum case this subject is labeled frequently as "nonstationary Casimir effect" or "dynamical Casimir effect"), from 1921 to October of 2000, with an emphasis on analytical results related to cavities with resonantly oscillating boundaries.

Sintering of ultrafine undoped SnO2 powder

Abstract: The sintering process of nanometric undoped SnO 2 powder was studied. No macroscopic shrinkage was observed during the sintening process. Grain growth kinetics investigation showed that surface diffusion is the dominant mechanism in the temperature range 500–1300°C. For temperatures higher than 1300°C, high weight loss was measured, suggesting evaporation–condensation as the dominant mass-transport mechanism. Thermogravimetric analysis (TG) and mass spectroscopy studies showed that the surface contamination of the SnO 2 particles by chemical species like H 2 O, OH − and CO 2 , has a strong influence on the role of mass transport controlled by surface diffusion.

Industrial crystallization and precipitation from solutions: state of the technique

Abstract: Crystallization and precipitation from solutions are responsible for 70% of all solid materials produced by the chemical industry. Competing with distillation as a separation and purification technique, their use is widespread. They operate at low temperatures with low energy consumption and yield with high purifications in one single step. Operational conditions largely determine product quality in terms of purity, filterability, flowability and reactivity. Producing a material with the desired quality often requires a sound knowledge of the elementary steps involved in the process: creation of supersaturation, nucleation, crystal growth, aggregation and other secondary processes. Mathematical models coupling these elementary processes to all particles in a crystallizer have been developed to design and optimize crystallizer operation. For precipitation, the spatial distribution of reactants and particles in the reactor is important; thus the tools of computational fluid dynamics are becoming increasingly important. For crystallization of organic chemicals, where incorporation of impurities and crystal shape are critical, molecular modeling has recently appeared as a useful tool. These theoretical developments must be coupled to experimental data specific to each material. Theories and experimental techniques of industrial crystallization and precipitation from solutions are reviewed, and recent developments are highlighted.

Effect of oxidizing and reducing atmospheres on the electrical properties of dense SnO2-based varistors

Abstract: The SnO 2 based varistor systems recently presented in the literature appear to have a promising potential in commercial applications. Experimental evidence shows that there is a dependence of nonlinear constant values with thermal treatment under different atmospheres. Thermal treatments in oxygen and nitrogen rich atmospheres at 900°C prove this dependence, indicating that the nonlinear constant values are significantly lower when the material is submitted to a nitrogen atmosphere. Moreover, electrical properties can be restored when the varistor is subjected to thermal treatment at the same temperature in an oxygen atmosphere, indicating that the mechanism seems to be reversible. This paper discusses this behavior focusing in the grain boundary region. Ta 2 O 5 mol% concentrations are also analyzed and the results indicate an optimum Ta 2 O 5 concentration of 0.05 mol% for the electrical properties ( α =44 and E B =6150 V cm −1 ).

Nonstationary Casimir Effect and analytical solutions for quantum fields in cavities with moving boundaries

Abstract: This is a review of publications on classical and quantum electrodynamics in cavities with moving boundaries (in the quantum case this subject is labeled frequently as "nonstationary Casimir effect" or "dynamical Casimir effect"), from 1921 to October of 2000, with an emphasis on analytical results related to cavities with resonantly oscillating boundaries.

Alterações na resistência à difusão de vapor das folhas e relações hídricas em aceroleiras submetidas a déficit de água

Abstract: Young sexually and assexually propagated Barbados cherry plants were submitted to water deficit (20 days without irrigation). During this period the accumulation of proline, water potential of branches, osmotic potential, the relative water content of leaves, the leaf diffusive resistance, the transpiration rate and leaf temperature in the cuvette were determined. In addition, photosynthetically active radiation (PAR) and vapor pressure deficit (VPD) were measured in the porometer cuvette. The concentration of proline for both types of plants began to increase on the fifth day without watering, and reached 38.1 times the concentration in the control plants grown from seeds and 26.4 times the concentration in grafted plants on the tenth day without watering. The lowest levels of leaf water potential in the plants suffering from severe water stress varied from -4.5 to -5.7 MPa, the lowest values being observed in the sexually propagated plants. These plants also showed the highest values for transpiration (0.9 mmol.m-2.s-1) and proline concentration (20.42 mg.g-1 DM), the lowest for relative water content of the leaves (38.4%) and diffusive resistance (940 s.m-1) at the end of the experiment. The Barbados cherry plants developed strategies for surviving drought, with differences between various characteristics, resulting from prolonged stress, which significantly influenced the parameters evaluated, with the exception of leaf temperature.

Model for sintering polydispersed glass particles

Abstract: We propose a model to describe the sintering kinetics of polydispersed glass particles, having no adjustable parameter. The model is based on three sintering stages: a pure ‘Frenkel’ (F) first step, a mixed ‘Frenkel/Mackenzie‐ Shuttleworth’ stage, and a third, pure ‘Mackenzie‐Shuttleworth’ (MS) step. The model considers sample shrinkage as the sum of the partial shrinkage of several clusters, each consisting of equally sized particles and each showing independent F or MS behavior. The overall set of clusters mimics the specimen’s real particle size distribution. We then introduce the concept of neck forming ability ‐ nr, which allows the formation of necks among particles of diAerent sizes, relaxing the clustering condition. Using experimental physical parameters: particle size distribution, viscosity, surface energy, and the theoretical nr, the model describes well the sintering kinetics of an alumino-borosilicate glass powder having polydispersed, irregular shaped particles in a variety of temperatures. The sintering kinetics of the real powder is slower, but not far from the calculated kinetics of a monodispersed distribution containing only particles of average size. Thus the model provides a tool for estimating the sintering kinetics of real glass powders, for any size distribution and temperature, thus minimizing the number of laboratory experiments. ” 2001 Elsevier Science B.V. All rights reserved.

Morphometric Analysis of the Intestine of Domestic Quails (Coturnix coturnix japonica) Treated with Different Levels of Dietary Calcium

Abstract: The aim of this study was to perform a morphometric analysis of the various parts of the intestine of the domestic quail. Twenty-four female quails (Coturnix coturnix japonica) aged 37 weeks were used and accommodated in laying cages for 12 weeks. Each group was fed a standardized diet containing different quantities of calcium: 2.0%, 2.5%, 3.0% and 3.5%. The birds were weighed, killed, and samples of 1 cm were collected from the duodenum, jejunum and ileum and submitted to the histological routine. The sections obtained were stained in haematoxylin & cosin (H&E). For morphometric analysis, 30 villi and 30 crypts of each segment of the small intestine were measured in order to determine the height and area of the villi, as well as the depth of the crypts. The results showed that although the integrity of the gastrointestinal tract was maintained in all the birds treated with the different calcium levels, a calcium level of 3.0% showed the most promise. as the levels of 2.0% and 2.5% did not cause any alteration in the intestinal tract. Furthermore, a calcium level of 3.5% led to a significant reduction in the height of the villosities, and in consequence reduced the digestive and absorptive capabilities.

Analysing emergency medical service ambulance deployment on a Brazilian highway using the hypercube model

Abstract: In this study we analyse the ambulance deployment of an emergency medical system on a Brazilian highway connecting the cities of Sao Paulo and Rio de Janeiro. Our focus is on the mean response time of the system to an emergency call, viewed as an important component of the user service. To evaluate the system performance we applied the hypercube model, a well-known tool for planning server-to-customer systems, which is based on spatially distributed queuing theory. The results showed that the model can be effective in supporting design and operational decisions, in particular to reduce the workload unbalancing among the ambulances.

Entomopathogenic nematodes: potential for exploration and use in South America

Abstract: Entomopathogenic nematodes have potential for biological control of insect pests. They are currently used for the control of soil and cryptic pests in North America, Europe, Asia and Australia. Entomopathogenic nematodes can be easily mass-produced and applied using conventional spray equipment. They have a broad host range and are safe to the environment. Due to the history of success with implementation of biological pest control programs, South American countries have a great opportunity to develop and implement the use of entomopathogenic nematodes. Recent emphasis on fruit and vegetable production in Brazil also stresses a need to implement safer and effective pest control methods. This paper provides an overview of recent developments in entomopathogenic nematode research and commercialization, evaluates their potential for use and exploration in Brazil and other South American countries, and makes recommendations for establishing entomopathogenic nematology.

Terrestrial Small Mammal Richness and Habitat Associations in an Amazon Forest–Cerrado Contact Zone1

Abstract: The Amazon Forest and the Cerrado of central Brazil share an extensive zone of integration. Each of these major ecosystems remains poorly studied; however, the composition of communities at the contact zone is even less well described. Small mammals were sampled during a ten-week period in a zone of contact between Amazonian forest and Cerrado. The vegetation in the area was a complex mixture of tropical and semi-deciduous forest, and grassland and savanna woodland formations. Mammals were marked and recaptured on 0.25- to 0.5-km transects and vouchers were collected. A total of 19 species was caught (13 rodents and 6 marsupials) in 4621 trap nights. Transitions from one vegetation type to another were abrupt with ecotones frequently < 5 m in width. The highest α-diversity was 7 species in cerrado. Ten of the 19 species were restricted to one habitat and 6 were restricted to two habitats. Three generalist grassland species occurred in more than two habitats, all variations of savanna. These data ...

Raman study of morphotropic phase boundary in PbZr 1 − x Ti x O 3 at low temperatures

Abstract: The Raman spectra of ${\mathrm{PbZr}}_{1\ensuremath{-}x}{\mathrm{Ti}}_{x}{\mathrm{O}}_{3}$ ceramics with titanium concentration varying between $x=0.40$ and 0.60 were measured at 7 K. By observing the concentration-frequency dependence of the vibrational modes, we identified the boundaries among the rhombohedral, monoclinic, and tetragonal ferroelectric phases. The analysis of the spectra was made in the view of group theory analysis making possible the assignment of some modes for the monoclinic phase.

Shrinkage characteristics of strawberries osmotically dehydrated in combination with microwave drying

Abstract: The subject of this paper is to study the shrinkage of strawberries as a function of the moisture ratio during microwave-convective drying. Strawberries were pre-treated and osmotically dehydrated and dried at power levels 0.1 and 0.2W/g, based on initial mass. The main results showed that the shrinkage has a linear relation with moisture ratio; the equivalent diameter of the strawberry has a reciprocal logarithmic function with moisture ratio; the change in volume was bigger for the fruits osmotically dehydrated than for the not osmotically dehydrated ones, power level exerts influence on shrinkage and equivalent diameter for pre-treated and osmotically dehydrated samples.