59 resultados para 250502 Physical Chemistry of Macromolecules


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After thirty two years in Brazil and retired from Universidade Estadual de Campinas the author wishes to present this account, a summary of a large part of the research in synthetic methodology developed by the research groups of Albert J. Kascheres and the author at Universidade Estadual de Campinas Chemistry Institute. Contributions have been made to the area of enaminones, diazocarbonyls, cyclopropenones and azirines.

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The presence of tin in the network of silicate glasses produces changes in several of their physico-chemical properties. Glasses with the composition (mol%) 22Na(2)O (.) 8CaO (.) 70SiO(2) containing up to 5 wt% of SnO2 were analyzed under several experimental techniques. Dilatometric measurements showed an increase of the glass transition temperature with increasing tin content, while the average thermal expansion coefficient is reduced. Vickers microhardness, density, and refractive index also increase with the tin content. Diffuse reflectance spectra in the infrared (DRIFT) showed that the presence of tin, even at low concentrations, is responsible for some structural changes since there is an increase of the bridging oxygen concentration. The doped glasses present a brown color and optical absorption spectra measurements are interpreted as being due to precipitation of tin in the form of colloidal particles during cooling of the melted glass. In the Na+ <-> K+ ion exchange process the presence of tin in the glass network hinders the diffusion of these ions. The diffusion coefficients of those ions were calculated by the Boltzmann-Matano technique, after concentration profiles obtained by EDS measurements. All results obtained present evidences that Sn4+ cation acts as a glass network former. (c) 2005 Elsevier B.V. All rights reserved.

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We analyse the properties of the Sp(1, R) model states using a basis obtained from the deformed harmonic oscillator wavefunctions. We make an Sp(1, R) calculation for C-12 and consider bases obtained from oblate, triaxial and prolate intrinsic states. The model states are given by angular momentum projection of vibrational phonons, which are associated with giant monopole and quadrupole resonances.

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Experimental studies were carried out to determine thermal conductivity (k), thermal diffusivity (alpha), specific heat at constant pressure (c(p)), and density (rho) of cooked ham as functions of both sample moisture content (M) and temperature (T). Thermal conductivity was measured using the heat-line-source probe, thermal diffusivity by Dickerson method, specific heat by differential scanning calorimeter, and density by pycnometer assembly. Temperature ranged from 3.0 degrees C to 74.0 degrees C, corresponding to the cooking process, and moisture ranged from 40.0 to 73.0% (w. b.). Equations are provided for alpha as a function of M, c(p) as a function of T, and rho as a function of both M and T. Results for thermal conductivity are compatible with those published in the literature.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Chemical analyses for biotites and their host rocks from the Cabreúva (three facies) and Salto (five facies) intrusions from the multiple-centered rapakivi Itu Complex, State of São Paulo, Brazil, are presented and compared. The Cabreúva intrusion comprises different kinds of mainly even-grained biotite and hornblende-bearing syenogranites, monzogranites and quartz syenites and the Salto intrusion several types of mainly porphyritic biotite syenogranites, some of them hornblende-bearing. The biotites from the Salto intrusion (S-micas) show a more restricted composition than those from the Cabreúva intrusion (C-micas). This reflects the chemical variability of the two bodies which is smaller in the Salto intrusion and larger in the Cabreúva pluton. In the AlIV x Fet/(Fet+Mg) diagram the S- and C-micas show similar AlIV contents, around 2.2-2.3, but C-micas have higher Fet/(Fet+Mg) ratios (0.7-0.9) compared to those of S-micas (0.5-0.6). In the Mg:(Al+Fe+3+Ti):(Fe+2+Mn) diagram the S-micas are defined as Fe+2-biotites and the C-micas occupy the area between the Fe+2-biotites and the siderophyllite/lepidomelane fields, slightly overlapping the latter. In the Al2O3 × FeOt, MgO × FeOt, Al2O3 x MgO and Alt x Mg diagrams, the S-micas always lie on the calc-alkaline/alkaline boundary (or in the subalkaline field) whereas the C-micas systematically plot in the alkaline field, reflecting the higher alkalis content of the Cabreúva intrusion. In the Fet/(Fet+Mg) x SiO2 diagram, the S-micas lie on a smooth line whereas the C-micas from the different facies are separated by distinct chemical gaps reflecting the major or minor chemical overlapping of the facies from the Salto and Cabreúva intrusions.

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This paper presents optical and electrical measurements on plasma generated by DC excited glow discharges in mixtures composed of 95% N2, 4.8% CH4 and 0.2% H2O at pressures varying from 1.064 mbar to 4.0 mbar. The discharges simulate the chemical reactions that may occur in Titan's atmosphere in the presence of meteorites and ice debris coming from Saturn's systems, assisted by cosmic rays and high energy charged particles. The results obtained from actinometric optical emission spectroscopy, combined with the results from a pulsed Langmuir probe, show that chemical species CH, CN, NH and OH are important precursors in the synthesis of the final solid products and that the chemical kinetics is essentially driven by electronic collision processes. It is shown that the presence of water is sufficient to produce complex solid products whose components are important in prebiotic compound synthesis. © 1998 Elsevier Science Ltd. All rights reserved.

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The solid solution 0.9PbMg 1/3Nb 2/3O 3-0.1PbTiO 3 is one of the most widely investigated relaxor ceramic, because of its high dielectric constant and low sintering temperatures. PMN-PT powders containing single perovskite phase were prepared by using a Timodified columbite precursor obtained by the polymeric precursor method. Such precursor reacts directly with stoichiometric amount of PbO to obtain pyrochlore-free PMN-PT powders. The structural effects of K additive included in the columbite precursor and 0.9PMN-0.1PT powders were also studied. The phase formation at each processing step was verified by XRD analysis, being these results used for the structural refinement by the Rietveld method. It was verified the addition of K in the columbite precursor promotes a slight increasing in the powder crystallinity. There was not a decrease in the amount of perovskite phase PMN-PT for 1mol% of K, and the particle and grain size were reduced, making this additive a powerful tool for grain size control.

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Purpose: The objective of this study was to evaluate the influence of the Grander technology in reducing the surface tension and contact angle of a self-etch adhesive system. Methods: Distilled water and Xeno III self-etch adhesive system (Dentsply) were modified by physical contact with the Flexible unit Grander system to revitalize water, for 48 hours, resulting in four groups: Group 1 - Xeno III under normal conditions; Group 2 - Xeno III modified by Grander; Group 3 - distilled water under normal conditions; Group 4 - distilled water system modified by the Grander system;. Surface tension and contact angle (dentin substrate and titanium plate) of the adhesive system and water in normal and Grander-modified conditions was measured with a goniometer. Data were analyzed by ANOVA and Tukey test (5%). Results: Grander technology reduced the surface tension of water but not of the adhesive system Xeno III. The contact angle property of the adhesive ystem was not affected. Conclusion: Grander technology did not interfere with the surface tension and contact angle physical properties of the Xeno III self-etch adhesive system. Copyright: © 2011 Gonçalves et al.;.

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Polymers mixtures as well as cross-linking reactions are approaches that have been used successfully to modulate the polymers characteristics in order to improve the control over drug release rate. High amylose and pectin are polysaccharides frequently used to prepare drug delivery systems. Since the drying technique can strongly influence the properties of such systems, the aim of this work was to characterize high amylose/pectin mixtures cross-linked with sodium trimetaphosphate and dried by different techniques-oven and lyophilization. The results showed that samples dried by lyophilization presented reduced particle size, higher porosity and higher swelling ability than the samples dried in oven. Besides, lower thermal stability and different diffraction patterns showed by the former particles should reflect the structural changes as a function of drying technique. © 2013 Informa Healthcare USA, Inc.

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Physical fractions (free light fraction, intra-aggregate light fraction and heavy fraction) of soil organic matter (SOM) are good indicators of soil quality for sustainable land use. The objective of this study was to evaluate the effect of cover crops on total organic carbon (TOC) and physical fractions of soil organic matter in soil under a no-tillage system (NTS) and a conventional tillage system (CTS, one plowing and two disking). A three-year field experiment was carried out as a cover crop-rice (Oryza sativa)-cover crop-rice rotation. Treatments included cover crops (Panicum maximum, Brachiaria ruziziensis, Brachiaria brizantha, and pearl millet (Pennisetum glaucum), fallow, till or no till. The SOM was physically fractionated in free light fraction (FLF), intra-aggregates light fraction (IALF) and heavy fraction (HF). The levels of C in whole soil were also evaluated, as well as C in the light fractions (FLF+IALF) and in the HF. Results indicated that concentrations of C in the FLF and IALF in surface soils (0-0.05m) were much higher (10.8 and 1.95gkg-1, respectively) than that in the 0.05-0.1m soil depth (7.68 and 1.54gkg-1, respectively) and in the 0.1-0.2m soil depth (4.98 and 1.24gkg-1, respectively). The NTS resulted in higher levels of FLF (12.2gkg-1) and IALF (2.19gkg-1) than with CTS (1.37-7.30gkg-1). Millet had the highest C (19.5gkg-1) and N (1.1gkg-1) concentrations in soil. There was an accumulation of TOC and total N in the surface soil with cover crops, and concentrations of TOC were higher in the HF (79.0%) than in the light fractions (21.0%). Although SOM changed little during the two years of this experiment, the various C fractions were significantly affected by the tillage treatments. We conclude that SOM physical fractionation allowed seeing significant differences caused by the soil management in the organic matter dynamics in a short period of time. © 2013 Elsevier B.V.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Soil physical quality is an important factor for the sustainability of agricultural systems. Thus, the aim of this study was to evaluate soil physical properties and soil organic carbon in a Typic Acrudox under an integrated crop-livestock-forest system. The experiment was carried out in Mato Grosso do Sul, Brazil. Treatments consisted of seven systems: integrated crop-livestock-forest, with 357 trees ha-1 and pasture height of 30 cm (CLF357-30); integrated crop-livestock-forest with 357 trees ha-1 and pasture height of 45 cm (CLF357-45); integrated crop-livestock-forest with 227 trees ha-1 and pasture height of 30 cm (CLF227-30); integrated crop-livestock-forest with 227 trees ha-1 and pasture height of 45 cm (CLF227-45); integrated crop-livestock with pasture height of 30 cm (CL30); integrated crop-livestock with pasture height of 45 cm (CL45) and native vegetation (NV). Soil properties were evaluated for the depths of 0-10 and 10-20 cm. All grazing treatments increased bulk density (r b) and penetration resistance (PR), and decreased total porosity (¦t) and macroporosity (¦ma), compared to NV. The values of r b (1.18-1.47 Mg m-3), ¦ma (0.14-0.17 m³ m-3) and PR (0.62-0.81 MPa) at the 0-10 cm depth were not restrictive to plant growth. The change in land use from NV to CL or CLF decreased soil organic carbon (SOC) and the soil organic carbon pool (SOCpool). All grazing treatments had a similar SOCpool at the 0-10 cm depth and were lower than that for NV (17.58 Mg ha-1).