972 resultados para PREFERRED TEMPERATURES
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Optical memories with long-term stability at high temperatures have long been pursued in azopolymers with photoinduced birefringence. In this study, we show that the residual birefringence in layer-by-layer (LbL) films made with poly[1-[4-(3-carboxy-4 hydroxyphenylazo)benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) alternated with poly(allylamine hydrochloride) (PAH) can be tuned by varying the extent of electrostatic interactions with film fabrication at different pHs for PAH. The dynamics of both writing and relaxation processes could be explained with a two-stage mechanism involving the orientation of the chromophores per se and the chain movement. Upon calculating the activation energies for these processes, we demonstrate semiquantitatively that reduced electrostatic interactions in films prepared at higher pH, for which PAH is less charged, are responsible for the longer stability at high temperatures. This is attributed to orientation of PAZO chromophores via cooperative aggregation, where the presence of counterions hindered relaxation.
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A 20% Pt3Sn/C catalyst was prepared by reduction with formic acid and used in a direct ethanol fuel cell at low temperatures. The electro-catalytic activity of this bimetallic catalyst was compared to that of a commercial 20% Pt/C catalyst. The PtSn catalyst showed better results in the investigated temperature range (30 degrees-70 degrees C). Generally, Sn promotes ethanol oxidation by adsorption of OH species at considerably lower potentials compared to Pt, allowing the occurrence of a bifunctional mechanism. The bimetallic catalyst was physico-chemically characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses. The presence of SnO2 in the bulk and surface of the catalyst was observed. It appears that SnO2 can enhance the ethanol electro-oxidation activity at low potentials due to the supply of oxygen-containing species for the oxidative removal of CO and CH3CO species adsorbed on adjacent Pt active sites.
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Egg parasitism of Trichogramma pretiosum strain RV when presented with eggs of Anticarsia gemmatalis and Pseudoplusia includens was investigated at 18, 20, 22, 25, 28, 30 and 32 degrees C. The number of eggs parasitized per day decreased for both hosts as a function of the age of parasitoids, reaching 80% of lifetime parasitism more rapidly as temperature increased; on the 4th day at 32 degrees C and on the 12th day at 18 degrees C. The lifetime number of parasitized P. includens eggs achieved by the parasitoid maintained at 20 degrees C (44.95 +/- 3.94) differed from the results recorded at 32 degrees C (28.5 +/- 1.33). Differently, the lifetime number of A. gemmatalis parasitized eggs did not differ among the temperatures. When T. pretiosum reached 100% of lifetime parasitism, each adult female had parasitized from 28.5 +/- 1.33 to 44.95 +/- 3.94 and from 29.58 +/- 2.80 to 45.36 +/- 4.50 P. includens and A. gemmatalis eggs, respectively. Also, the longevity of these adult T. pretiosum females, for which P. includens or A. gemmatalis eggs were offered, was inversely correlated with temperature. Not only were the survival curves of those adult T. pretiosum females of type I when they were presented with eggs of A. gemmatalis but also with eggs of P. includens, i.e., there was an increase in the mortality rate with time as the temperature increased. In conclusion, T. pretiosum strain RV parasitism was impacted by temperature when on both host eggs; however, the parasitoid still exhibited high survival and, more importantly, high number of parasitized A. gemmatalis and P. includens eggs even at the extremes tested temperatures of 18 and 32 degrees C. Those results indicate that T. pretiosum strain RV might be well adapted to this studied temperature range and, thus, be potentially suitable for use in biological control programs of P. includens and A. gemmatalis in different geographical areas that fits in this range. It is important to emphasize the results here presented are from laboratory studies and, therefore, field trials still need to be carried out in the future with this strain in order to support the full development of the technology intend to use this egg parasitoid in soybean fields worldwide. (C) 2011 Elsevier Inc. All rights reserved.
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This study determined the ability of psychrotrophic Clostridium strains isolated from vacuum-packaged beefs and abattoir environments to cause 'blown-pack' spoilage of vacuum-packaged beef stored at 2 and 15 degrees C. The influence of shrinking temperatures (83, 84 and 87 degrees C) and vacuum pressure (6 and 9 mbar) on the occurrence of such spoilage as well as the effects of simulated transportation (500 km) on the integrity of packages was determined. At 15 degrees C and 2 degrees C, twelve and six strains caused 'blown-pack' spoilage, respectively. The combination of vacuum pressure (9 mbar) combined with shrinking temperature (87 degrees C) retarded the occurrence of spoilage. The simulated transportation under the experimental conditions did not affect the integrity of packages. More studies that assess the factors that may contribute for the occurrence of 'blown-pack' spoilage should be performed to avoid the occurrence of such spoilage during its shelf-life. (C) 2012 Elsevier Ltd. All rights reserved.
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The kinetics of sugar cane bagasse cellulose saccharification and the decomposition of glucose under extremely low acid (ELA) conditions, (0.07%), 0.14%, and 0.28% H2SO4, and at high temperatures were investigated using batch reactors. The first-order rate constants were obtained by weight loss, remaining glucose, and fitting glucose concentration profiles determined with HPLC using the Saeman model. The maximum glucose yields reached 67.6% (200 degrees C, 0.07% H2SO4, 30 min), 69.8% (210 degrees C, 0.14% H2SO4, 10 min), and 67.3% (210 degrees C, 0.28% H2SO4, 6 min). ELA conditions produced remarkable glucose yields when applied to bagasse cellulose. The first-order rate constants were used to calculate activation energies and extrathermodynamic parameters to elucidate the reaction mechanism under ELA conditions. The effect of acid concentration on cellulose hydrolysis and glucose decomposition was also investigated. The observed activation energies and reaction orders with respect to hydronium ion for cellulose hydrolysis and glucose decomposition were 184.9 and 124.5 kJ/mol and 1.27 and 0.75, respectively.
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Recent studies predict that several lineages of tropical animals are at particular risk given current estimates of global climate change. Yet, much uncertainty exists on the effects of climate shifts in ectothermic species from cool temperate regions such as Patagonia. In this study, we focus on the impact of environmental temperature on growth, age at sexual maturity, and life-span of the Patagonian gecko Homonota darwini. Skeletochronological methods were used to assess the bone growth rates Of individuals from three populations at different geographic and temporal scales: two populations from Chubut (warm site; 1941 and 2010) and one population from Rio Negro (cold site; 1997-1998). Populations displayed similar bone arrangement and the growth patterns fit a von Bertalanffy curve. Three populations attained reproductive size at a minimum age of 3 yr, but at the cold site two specimens were shown to mature in 4 yr. We found no differences in juvenile growth rates in body size or bone zone width between juveniles of 1 to 3 yr of age from the 1941 warm site and the 2010 warm site. However, these traits appeared to be higher at these two warm sites than at the cold site, which is consistent with the climatic differences among the three localities. Our results suggest that higher temperatures positively affect growth, denoting that global warming might benefit H. darwini, especially the southern populations.
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The thermal limits of individual animals were originally proposed as a link between animal physiology and thermal ecology. Although this link is valid in theory, the evaluation of physiological tolerances involves some problems that are the focus of this study. One rationale was that heating rates shall influence upper critical limits, so that ecological thermal limits need to consider experimental heating rates. In addition, if thermal limits are not surpassed in experiments, subsequent tests of the same individual should yield similar results or produce evidence of hardening. Finally, several non-controlled variables such as time under experimental conditions and procedures may affect results. To analyze these issues we conducted an integrative study of upper critical temperatures in a single species, the ant Atta sexdens rubropiosa, an animal model providing large numbers of individuals of diverse sizes but similar genetic makeup. Our specific aims were to test the 1) influence of heating rates in the experimental evaluation of upper critical temperature, 2) assumptions of absence of physical damage and reproducibility, and 3) sources of variance often overlooked in the thermal-limits literature; and 4) to introduce some experimental approaches that may help researchers to separate physiological and methodological issues. The upper thermal limits were influenced by both heating rates and body mass. In the latter case, the effect was physiological rather than methodological. The critical temperature decreased during subsequent tests performed on the same individual ants, even one week after the initial test. Accordingly, upper thermal limits may have been overestimated by our (and typical) protocols. Heating rates, body mass, procedures independent of temperature and other variables may affect the estimation of upper critical temperatures. Therefore, based on our data, we offer suggestions to enhance the quality of measurements, and offer recommendations to authors aiming to compile and analyze databases from the literature.
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Quality of fresh-cut carambola (Averrhoa carambola L) is related to many chemical and biochemical variables especially those involved with softening and browning, both influenced by storage temperature. To study these effects, a multivariate analysis was used to evaluate slices packaged in vacuum-sealed polyolefin bags, and stored at 2.5 degrees C, 5 degrees C and 10 degrees C, for up to 16 d. The quality of slices at each temperature was correlated with the duration of storage, O(2) and CO(2) concentration in the package, physical chemical constituents, and activity of enzymes involved in softening (PG) and browning (PPO) metabolism. Three quality groups were identified by hierarchical cluster analysis, and the classification of the components within each of these groups was obtained from a principal component analysis (PCA). The characterization of samples by PCA clearly distinguished acceptable and non-acceptable slices. According to PCA, acceptable slices presented higher ascorbic acid content, greater hue angles ((o)h) and final lightness (L-5) in the first principal component (PC1). On the other hand, non-acceptable slices presented higher total pectin content. PPO activity in the PC1. Non-acceptable slices also presented higher soluble pectin content, increased pectin solubilisation and higher CO(2) concentration in the second principal component (PC2) whereas acceptable slices showed lower total sugar content. The hierarchical cluster and PCA analyses were useful for discriminating the quality of slices stored at different temperatures. (C) 2011 Elsevier B.V. All rights reserved.
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The Apiai gabbro-norite is a massive fine-grained Neoproterozoic intrusion emplaced in a core of synformal structure that deforms low-grade marine metasedimentary rocks of the Ribeira Belt of south-eastern Brazil. The lack of visible magmatic layering or any internal fabric has been a major limitation in deciding whether the emplacement occurred before or after the regional folding. To assist in the tectonic interpretations, we combine low-field anisotropy of magnetic susceptibility (AMS) and silicate shape preferred orientation (SPO) to reveal the internal structure of the mafic intrusion. Magnetic data indicate a mean susceptibility of about 10(-2) SI and a mean anisotropy degree (P) of about 1.08, essentially yielded by titanomagnetite. The magnetic and silicate foliations for P >= 1.10 are parallel to each other, while the lineations tend to scatter on the foliation plane, in agreement with the dominant oblate symmetry of the AMS and SPO ellipsoids. For lower P values, the magnetic and silicate fabrics vary from coaxial to oblique, and for P <= 1.05, their shapes and orientations can be quite distinct. The crystal size distribution (CSD) of plagioclase for P > 1.05 is log linear, in agreement with a bulk simple crystallisation history. These results combined show that for a strong SPO, corresponding to a magnetic anisotropy above 1.10, AMS is a reliable indicator of the magmatic fabric. They indicate that the Apiai gabbro-norite consists of sill-like body that was inclined gently to the north by the regional folding.
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The growing demand for knowledge about the effect of high temperatures on structures has stimulated increasing research worldwide. This article presents experimental results for short composite steel and concrete columns subjected to high temperatures in ovens with or without an axial compression load, numerically analyzes the temperature distribution in these columns after 30 and 60 minutes and compares them with experimental results. The models consist of concrete-filled tubes of three different thicknesses and two different diameters, and the concrete fill has conventional properties that remained constant for all of the models. The stress-strain behavior of the composite columns was altered after exposure to high temperatures relative to the same columns at room temperature, which was most evident in the 60-minute tests due to the higher temperatures reached. The computational analysis adopted temperature rise curves that were obtained experimentally.
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Studies of skin wound healing in crocodilians are necessary given the frequent occurrence of cannibalism in intensive farming systems. Air temperature affects tissue recovery because crocodilians are ectothermic. Therefore, the kinetics of skin wound healing in Caiman yacare were examined at temperatures of 33°C and 23°C. Sixteen caiman were selected and divided into two groups of eight maintained at 23°C or 33°C. The studied individuals' scars were photographed after 1, 2, 3, 7, 15 and 30 days of the experimental conditions, and samples were collected for histological processing after 3, 7, 15 and 30 days. Macroscopically, the blood clot (heterophilic granuloma) noticeably remained in place covering the wound longer for the caiman kept at 23°C. Microscopically, the temperature of 23°C slowed epidermal migration and skin repair. Comparatively, new blood vessels, labeled using von Willebrand factor (vWF) antibody staining, were more frequently found in the scars of the 33°C group. The collagen fibers in the dermis were denser in the 33°C treatment. Considering the delayed healing at 23°C, producers are recommended to keep wounded animals at 33°C, especially when tanks are cold, to enable rapid wound closure and better repair of collagen fibers because such lesions tend to compromise the use of their skin as leather.
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Nanofiltration (NF) is a pressure-driven membrane process, intermediate between reverse osmosis and ultrafiltration. Commercially available polymeric membranes have been used in a wide range of applications, such as drinking, process industry and waste water treatment. For all the applications requiring high stability and harsh washing procedures inorganic membranes are preferred due to their high chemical inertia. Typically, γ – Al2O3 as well as TiO2 and ZrO2 selective layers are used; the latter show higher chemical stability in a wide range of pH and temperatures. In this work the experimental characterization of two different type of membrane has been performed in order to investigate permeation properties, separation performance and efficiency with aqueous solutions containing strong inorganic electrolytes. The influence of salt concentration and feed pH as well as the role of concentration polarization and electrolyte type on the membrane behavior are investigated. Experimentation was performed testing a multi–layer structured NF membrane in α-Al2O3, TiO2 and ZrO2, and a polymeric membrane, in polyamide supported on polysulfone, with binary aqueous solutions containing NaCl, Na2SO4 or CaCl2; the effect of salt composition and pH in the feed side was studied both on flux and salt rejection. All the NF experimental data available for the two membranes were used to evaluate the volumetric membrane charge (X) corresponding to each operative conditions investigated, through the Donnan Steric Pore Model and Dielectric Exclusion (DSPM&DE). The results obtained allow to understand which are the main phenomena at the basis of the different behaviors observed.
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Water is a safe, harmless, and environmentally benign solvent. From an eco-sustainable chemistry perspective, the use of water instead of organic solvent is preferred to decrease environmental contamination. Moreover, water has unique physical and chemical properties, such as high dielectric constant and high cohesive energy density compared to most organic solvents. The different interactions between water and substrates, make water an interesting candidate as a solvent or co-solvent from an industrial and laboratory perspective. In this regard, organic reactions in aqueous media are of current interest. In addition, from practical and synthetic standpoints, a great advantage of using water is immediately evident, since it does not require any preliminary drying process. This thesis was found on this aspect of chemical research, with particular attention to the mechanisms which control organo and bio-catalysis outcome. The first part of the study was focused on the aldol reaction. In particular, for the first time it has been analyzed for the first time the stereoselectivity of the condensation reaction between 3-pyridincarbaldehyde and the cyclohexanone, catalyzed by morpholine and 4-tertbutyldimethylsiloxyproline, using water as sole solvent. This interest has resulted in countless works appeared in the literature concerning the use of proline derivatives as effective catalysts in organic aqueous environment. These studies showed good enantio and diastereoselectivities but they did not present an in depth study of the reaction mechanism. The analysis of the products diastereomeric ratios through the Eyring equation allowed to compare the activation parameters (ΔΔH≠ and ΔΔS≠) of the diastereomeric reaction paths, and to compare the different type of catalysis. While morpholine showed constant diasteromeric ratio at all temperatures, the O(TBS)-L-proline, showed a non-linear Eyring diagram, with two linear trends and the presence of an inversion temperature (Tinv) at 53 ° C, which denotes the presence of solvation effects by water. A pH-dependent study allowed to identify two different reaction mechanisms, and in the case of O(TBS)-L-proline, to ensure the formation of an enaminic species, as a keyelement in the stereoselective process. Moreover, it has been studied the possibility of using the 6- aminopenicillanic acid (6-APA) as amino acid-type catalyst for aldol condensation between cyclohexanone and aromatic aldehydes. A detailed analysis of the catalyst regarding its behavior in different organic solvents and pH, allowed to prove its potential as a candidate for green catalysis. Best results were obtained in neat conditions, where 6-APA proved to be an effective catalyst in terms of yields. The catalyst performance in terms of enantio- and diastereo-selectivity, was impaired by the competition between two different catalytic mechanisms: one via imine-enamine mechanism and one via a Bronsted-acid catalysis. The last part of the thesis was dedicated to the enzymatic catalysis, with particular attention to the use of an enzyme belonging to the class of alcohol dehydrogenase, the Horse Liver Alcohol Dehydrogenase (HLADH) which was selected and used in the enantioselective reduction of aldehydes to enantiopure arylpropylic alcohols. This enzyme has showed an excellent responsiveness to this type of aldehydes and a good tolerance toward organic solvents. Moreover, the fast keto-enolic equilibrium of this class of aldehydes that induce the stereocentre racemization, allows the dynamic-kinetic resolution (DKR) to give the enantiopure alcohol. By analyzing the different reaction parameters, especially the pH and the amount of enzyme, and adding a small percentage of organic solvent, it was possible to control all the parameters involved in the reaction. The excellent enatioselectivity of HLADH along with the DKR of arylpropionic aldehydes, allowed to obtain the corresponding alcohols in quantitative yields and with an optical purity ranging from 64% to >99%.