Determination of site-site distance and site concentration within polymer beads: A combined swelling-electron paramagnetic resonance study

[GRAPHICS]This work proposes a combined swelling-electron paramagnetic resonance (EPR) approach aiming at determining some unusual polymer solvation parameters relevant for chemical processes occurring inside beads. Batches of benzhydrylamine-resin (BHAR), a copolymer of styrene-1% divinylbenzene containing phenylmethylamine groups were, labeled with the paramagnetic amino acid 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amine-4-carboxylic acid (TOAC), and their swelling properties and EPR spectra were examined in DCM and DMF. By taking into account the BHARs labeling degrees, the corresponding swelling values, and some polymer structural characteristics, it was possible to calculate polymer swelling parameters, among them, the volume and the number of sites per bead, site-site distances and site concentration. The latter values ranged from 17 to 170 angstrom and from 0.4 to 550 mM, respectively. EPR spectroscopy was applied to validate the multistep calculation strategy of these swelling parameters. Spin-spin interaction was detected in the labeled resins at site-site distances less than approximately 60 A or probe concentrations higher than approximately 1 x 10(-2) M, in close agreement with the values obtained for the spin probe free in solution. Complementarily, the yield of coupling reactions in different resins indicated that the greater the inter-site distance or the lower the site concentration, the faster the reaction. The results suggested that the model and the experimental measurements developed for the determination of solvation parameters represent a relevant step forward for the deeper understanding and improvement of polymer-related processes.

Thermal analysis of chitosan based networks

In this work two kinds of material were studied: chitosan cross-linked with glutaraldehyde and in a blend with PEO. The resulting products as well as chitosan and PEO raw materials, were analyzed by TG/DTG, DSC and DMTA to determinate the in?uence of cross-linking and PEO addition on thermal properties of the resulting materials. It was observed by thermogravimetry that the water-polymer interaction will be different for the cross-linked material compared to the blend, according to the specific site availability. The in?uence of such modifications (cross-linking and PEO addition), on chitosan thermal stability was also studied. The DSC results showed a good agreement with the TG/DTG results, reinforcing the interpretation given for TG/DTG results. DMTA results indicate that glass transition temperature is around 50 degrees C for the polymer under study. (c) 2005 Elsevier Ltd. All rights reserved.

Three-dimensional finite element analysis of MHD duct flow by the penalty function formulation

A numerical scheme based on the Finite Element Method (FEM) is presented to calculate the full solution of a three-dimensional steady magnetohydrodynamic (MHD) flow with moderately high Hartmann numbers and interaction parameters. An incompressible, viscous and electrically conducting liquid-metal is considered. Assuming a low magnetic Reynolds number, the solution method solves the coupled Navier-Stokes and Maxwell's equations through the use of a penalty function method. Results are presented for Hartmann numbers in the range 10(2)-10(3).

Blends of cross-linked high amylose starch/pectin loaded with diclofenac

Polymers blends represent an important approach to obtain materials with modulated properties to reach different and desired properties in designing drug delivery systems in order to fulfill therapeutic needs. The aim of this work was to evaluate the influence of drug loading and polymer ratio on the physicochemical properties of microparticles of cross-linked high amylose starch-pectin blends loaded with diclofenac for further application in controlled drug delivery systems. Thermal analysis and X-ray diffractograms evidenced the occurrence of drug-polymer interactions and the former pointed also to an increase in thermal stability due to drug loading. The rheological properties demonstrated that drug loading resulted in formation of weaker gels while the increase of pectin ratio contributes to origin stronger structures. © 2012 Elsevier Ltd.

Stable, mobile, dark-in-bright, dipolar Bose-Einstein-condensate solitons

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

Stable and mobile excited two-dimensional dipolar Bose-Einstein condensate solitons

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

Bright dipolar Bose-Einstein-condensate soliton mobile in a direction perpendicular to polarization

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

Redução de empeno em barra trefiladas do aço SAE 9254

In this paper we study the process of manufacture of wire drawn steel bars 9254, from rolled wire rod. These bars are used in the automotive industry for the manufacture of coil springs, which make up the system damping of several vehicles. The wire drawing process consists of the steps of pre-straightening, shot peening, drawing, cutting and polishing. The study aims to search for the configuration of process variables, which present the best result with respect to bending. To this were maintained settings prestraightening and mechanical stripping and varied angles and stringer polish being studied to replace the spinneret with a working angle, for a string with two working angles. To assist in the analysis of the results was the tool used DOE Software Minitab, which assesses the variation in results according to each parameter and the interaction parameters. It was thus possible to determine the best condition for wire drawing

Vector solitons in a spin-orbit-coupled spin-2 Bose-Einstein condensate

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

Study of the interaction between cardiolipin bilayers and methylene blue in polymer-based Layer-by-Layer and Langmuir films applied as membrane mimetic systems

An increase of the reports involving mimetic systems has been observed. Briefly, these systems use biological phospholipids to exploit specific interactions between membrane-models and drugs. Here, the Layer-by-Layer (LbL) and Langmuir techniques were used to investigate the interaction between cardiolipin (CLP-negative phospholipid) and a cationic-like drug methylene blue (MB). Supported by a cationic polyelectrolyte (PAH), LbL films containing PAH/(CLP + MB) and PAH/(CLP + MB + AgNP) were grown up to 14 bilayers. The optical microscopy analysis revealed a decrease of the CLP vesicle sizes in the presence of MB as a possible consequence of the MB action onto the mechanical properties of the CLP membrane. From FTIR spectra, changes mainly related to peak position and band intensity and shape were observed in the spectra from PAH/CLP when in the presence of MB. The latter supports that the interactions between the phosphate and amine charged groups from CLP and PAH, respectively, established during the LbL film fabrication, besides the CLP hydrocarbon environment, are influenced by the presence of MB. Using the micro-Raman technique, a chemical mapping was build based on MB spectrum by resonance Raman scattering (RRS) and surface-enhanced resonance Raman scattering (SERRS). The later phenomenon was activated by Ag nanoparticles (AgNPs) trapped within the LbL film allowing collecting spectra for a single bilayer of PAH/(CLP + MB + AgNP). A rough estimation showed a SERRS amplification of 10(3) in comparison to RRS spectra. As a complementary approach, Langmuir films of CLP in the presence of co-spread MB were investigated through surface pressure vs mean molecular area (pi-A) isotherms. The results showed that for concentrations of MB below 100 mol%, the drug is expelled to water subphase for high values of surface pressure (condensed phase). For concentration at 100% and higher, the MB keeps bound to CLP floating monolayer. (C) 2010 Elsevier B.V. All rights reserved.

Consequences of dark matter-dark energy interaction on cosmological parameters derived from type Ia supernova data

Models where the dark matter component of the Universe interacts with the dark energy field have been proposed as a solution to the cosmic coincidence problem, since in the attractor regime both dark energy and dark matter scale in the same way. In these models the mass of the cold dark matter particles is a function of the dark energy field responsible for the present acceleration of the Universe, and different scenarios can be parametrized by how the mass of the cold dark matter particles evolves with time. In this article we study the impact of a constant coupling delta between dark energy and dark matter on the determination of a redshift dependent dark energy equation of state w(DE)(z) and on the dark matter density today from SNIa data. We derive an analytical expression for the luminosity distance in this case. In particular, we show that the presence of such a coupling increases the tension between the cosmic microwave background data from the analysis of the shift parameter in models with constant w(DE) and SNIa data for realistic values of the present dark matter density fraction. Thus, an independent measurement of the present dark matter density can place constraints on models with interacting dark energy.

Application of Nonisothermal Cure Kinetics to the Interaction of Poly(ethylene terephthalate) with Alkyd Resin Varnish

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Kinetic parameters of polymer degradation by SAPO-37

High density poly(ethylene) has been submitted to thermal degradation alone, and in the presence of silicoaluminophosphate SAPO-37. The processes were carried out in a reactor connected on line to a gas chromatograph/mass spectrometer in order to analyze the evolved products. Polymer degradation was also evaluated by thermogravimetry, from room temperature until 800 degreesC, under nitrogen dynamic atmosphere, with multiple heating rates. From TG curves, the activation energy related to degradation process was calculated using the Flynn and Wall multiple heating rate kinetic model for pure polymer (PE) and for polymer in the presence of catalyst (PE/S37). SAPO-37 showed good selectivity for low molecular mass hydrocarbons in PE catalytic degradation.

Spectroscopic study of the interaction of Nd3+ with amino acids: Phenomenological 4f-4f intensity parameters

We have studied the bevahior of the phenomenological 4f-4f intensity parameters in compounds of the Nd ion with glycine, L-aspartic acid, L-glutamic acid, L-histidine, DL-malic acid and Aspartame™ in aqueous solution, as a function of the pK values and partial charges on the oxygens of the carboxylate groups of these molecules. The results are discussed and qualitatively interpreted in terms of the forced electric dipole and dynamic coupling mechanisms of the 4f-4f intensities, thus indicating that the forced electric dipole mechanism is dominant.

Genotype-environment interaction for post-weaning traits in Nellore beef cattle

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)