Xylan from corn cobs, a promising polymer for drug delivery: Production and characterization

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Modified LPE system used to diffuse Cd to obtain InSb infrared detectors

We are presenting here p/n junctions obtained with a modified opened liquid-phase epitaxy (LPE) system, used to diffuse indium antimonide (InSb) doped with Cd over InSb doped with Te wafers, in order to make InSb infrared (IR) sensors. This technique has several advantages: the diffusion can be performed in bigger substrate areas improving the device production; this method decreases the device manipulation, decreasing human mistakes and increasing the process reproducibility. The opened LPE in this work produced sensors in the first case with vapor of the diffusion material, coming from a microholed carbon boat full of the diffusion material, over which is positioned the substrate at atmospheric pressure. In the second, the diffusion material is on the bottom of a quartz recipient, and the InSb/Te wafer works as its cover, and vacuum was used. The IR sensors produced with the first method measured 8.9 x 10(7) cm Hz(1/2)/W as detectivity value and higher IR spectral response at 4.6 mu m, and those produced with the second 2.8 x 10(9) cm Hz(1/2)/W, at 4.4 mu m. Besides the electrical-optical properties, the structural properties of diffused layers were investigated by X-ray diffraction (XRD), scanning electron and atomic force microscopy (SEM, AFM), energy-dispersive and secondary ion mass spectroscopy (EDS, SIMS). (C) 2007 Elsevier B.V. All rights reserved.

Alquilação redutiva da quitosana a partir do glutaraldeído e 3-amino-1-pr

Chitosan derivatives were prepared by reductive alkylation using glutaraldehyde and 3-amino-1-propanol. The reducing agent used was the sodium borohydride. Tests of solubility, stability and viscosity were performed in order to evaluate these parameters effects in the reaction conditions (molar ratio of the reactants and presence of nitrogen in the reaction system). The molecular structure of commercial chitosan was determined by infrared (IR) and hydrogen nuclear magnetic resonance spectroscopy (1H NMR). The intrinsic viscosity and average molecular weight of the chitosan were determined by viscosimetry in 0.3 M acetic acid aqueous solution 0.2 M sodium acetate at 25 ºC. The derivatives of chitosan soluble in aqueous acidic medium were characterized by 1H NMR. The rheological behavior of the chitosan and of the derivative of chitosan (sample QV), which presented the largest viscosity, were studied as a function of polymer concentration, temperature and ionic strength of the medium. The results of characterization of the commercial chitosan (the degree of deacetylation obtained equal 78.45 %) used in this work confirmed a sample of low molar weight (Mv = 3.57 x 104 g/mol) and low viscosity (intrinsic viscosity = 213.56 mL/g). The chemical modification of the chitosan resulted in derivatives with thickening action. The spectra of 1H NMR of the soluble derivatives in acid aqueous medium suggested the presence of hydrophobic groups grafted into chitosan in function of the chemical modification. The solubility of the derivatives of chitosan in 0.25 M acetic acid aqueous solution decreased with increase of the molar ratio of the glutaraldehyde and 3-amino-1-propanol in relation to the chitosan. The presence of nitrogen and larger amount of reducing agent in reaction system contributed to the increase of the solubility, the stability and the viscosity of the systems. The viscosity of the polymeric suspensions in function of the shear rate increased significantly with polymer concentration, suggesting the formation of strong intermolecular associations. The chitosan presented pseudoplastic behavior with the increase in polymer concentration at a low shear rate. The derivative QV presented pseudoplastic behavior at all concentrations used and in a large range of shear rate. The viscosity of chitosan in solution decreased with an increase of the temperature and with the presence of salt. However, there was an increase of the viscosity of the chitosan solution at higher temperature (65 ºC) and ionic strength of the medium which were promoted by hydrophobic associating of the acetamide groups. The solutions of the chitosan derivatives (sample QV) were significantly more viscous than chitosan solution and showed higher thermal stability in the presence of salt as a function of the hydrophobic groups grafted into chitosan backbone

Infrared studies of the monoclinic-tetragonal phase transition in Pb(Zr, Ti)O-3 ceramics

Recently, the observation of a new monoclinic phase in the PbZr1-xTixO3 (PZT) system in the vicinity of the morphotropic phase boundary was reported. Investigations of this new phase were reported using different techniques such as high-resolution synchrotron x-ray powder diffraction and Raman spectroscopy. In this work, the monoclinic --> tetragonal phase transition in PbZr0.50Ti0.50O3 ceramics was studied using infrared spectroscopy between 1000 and 400 cm(-1). The four possible nu(1)-stretching modes (Ti-O and Zr-O stretch) in the BO6 octahedron in the ABO(3) structure of PZT in this region were monitored as a function of temperature. The lower-frequency mode nu(1)-(Zr-O) remains practically unaltered, while both intermediate nu(1)-(Ti-O) modes decrease linearly as temperature increases from 89 to 263 K. In contrast, the higher-frequency nu(1)-(Ti-O) and nu(1)-(Zr-O) modes present anomalous behaviour around 178 K. The singularity observed at this mode was associated with the monoclinic --> tetragonal phase transition in PbZr0.50Ti0.50O3 ceramics.

The vinyl bromide optically pumped far infrared laser: New large offset emissions

We present the results of a study on vinyl bromide for the search for new far infrared (FIR) laser lines. As the pump source, we use a CW waveguide CO2 laser with a tunability of 290 MHz around each line in order to pump large offset vibrational transitions. As a consequence, we obtained 28 new FIR laser emissions; 24 of them have wavelengths greater than 500 mum and are, therefore, suitable to be used in high-field EPR spectroscopy, For each of the new lines, we give the wavelength, the offset of the pumping transition with respect to the center Frequency of the CO2 emission, the polarization relative to that of the pumping laser line, the operating pressure, and the relative intensity. We also present a catalog including data of all of the FIR laser lines observed from this molecule up to now.

Estudo cinético da degradação térmica e catalítica de petróleo pesado usando Al-MCM-41

The mesoporous nanostructured materials have been studied for application in the oil industry, in particular Al-MCM-41, due to the surface area around 800 to 1.000 m2 g-1 and, pore diameters ranging from 2 to 10 nm, suitable for catalysis to large molecules such as heavy oil. The MCM-41 has been synthesized by hydrothermal method, on which aluminum was added, in the ratio Si/Al equal to 50, to increase the generation of active acid sites in the nanotubes. The catalyst was characterized by X-ray diffraction (XRD), surface area by the BET method and, the average pore volume BJH method using the N2 adsorption, absorption spectroscopy in the infrared Fourier Transform (FT-IR) and determination of surface acidity with application of a probe molecule - n-butylamine. The catalyst showed well-defined structural properties and consistent with the literature. The overall objective was to test the Al-MCM-41 as catalyst and thermogravimetric perform tests, using two samples of heavy oil with API º equal to 14.0 and 18.5. Assays were performed using a temperature range of 30-900 ° C and heating ratios (β) ranging from 5, 10 and 20 °C min-1.The aim was to verify the thermogravimetric profiles of these oils when subjected to the action of the catalyst Al- MCM-41. Therefore, the percentage ranged catalyst applied 1, 3, 5, 10 and 20 wt%, and from the TG data were applied two different kinetic models: Ozawa-Flynn-Wall (OFW) and Kissinger-Akahrira-Sunose (KAS).The apparent activation energies found for both models had similar values and were lower for the second event of mass loss known as cracking zone, indicating a more effective performance of Al-MCM-41 in that area. Furthermore, there was a more pronounced reduction in the value of activation energy for between 10 and 20% by weight of the oil-catalyst mixture. It was concluded that the Al-MCM-41 catalyst has applicability in heavy oils to reduce the apparent activation energy of a catalyst-oil system, and the best result with 20% by weight of Al-MCM-41

Síntese de catalisadores nanoporosos na ausência total e parcial de direcionadores orgânicos para pirólise catalítica de óleos pesados e intermediários

The processing of heavy oil produced in Brazil is an emergency action and a strategic plan to obtain self-sufficiency and economic surpluses. Seen in these terms, it is indispensable to invest in research to obtain new catalysts for obtaining light fraction of hydrocarbons from heavy fractions of petroleum. This dissertation for the degree of Doctor of Philosophy reports the materials preparation that combine the high catalytic activity of zeolites with the greater accessibility of the mesoporosity, more particularly the HZSM-5/MCM-41 hybrid, done by synthesis processes with less environmental impact than conventional ones. Innovative methodologies were developed for the synthesis of micro-mesoporous hybrid material by dual templating mechanism and from crystalline zeolitic aluminosilicate in the absence of organic template. The synthesis of hybrid with pore bimodal distribution took place from one-single organic directing agent aimed to eliminate the use of organic templates, acids of any kind or organic solvents like templating agent of crystalline zeolitic aluminosilicate together with temperature-programmed microwave-assisted, making the experimental procedures of preparation most practical and easy, with good reproducibility and low cost. The study about crystalline zeolitic aluminosilicate in the absence of organic template, especially MFI type, is based on use of H2O and Na+ cation playing a structural directing role in place of an organic template. Advanced characterization techniques such as X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Highresolution Transmission Electron Microscopy (HRTEM), Adsorption of N2 and CO2, kinetic studies by Thermogravimetric Analysis (TGA) and Pyrolysis coupled to Gas Chromatography/Mass Spectrometry (Pyrolysis-GC/MS) were employed in order to evaluate the synthesized materials. Achieve the proposed objectives, has made available a set of new methodologies for the synthesis of zeolite and hybrid micro-mesoporous material, these suitable for catalytic pyrolysis of heavy oils aimed at producing light fraction

Influência da geometria e umidade de colunas de solo na biodegradação de filmes de PCL

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

Biodegradation of a polylactic acid/polyvinyl chloride blend in soil

This study investigated the microbial action in soil on poly(L-lactic acid) (PLLA) and polyvinyl chloride (PVC) films and a PLLA/PVC 7 : 3 blend, using Fourier transform infrared spectroscopy (FTIR), contact angle and scanning electron microscopy (SEM). The films (50 mu m) were obtained from the evaporation of dichloromethane solutions and buried in soil columns, in controlled conditions, for 120 days. The results showed that the surface of the PLLA films and blend became 18 and 31% more hydrophilic, respectively. The morphology of the films also changed after 120 days of microbial treatment, particularly that of the PLLA phase in the blend, confirmed by structural and conformational changes in the FTIR CO region at 12001000 cm1 and an increase in the relative intensity of the band at 1773 cm1, which was attributed to C O group vibration due to a rotational isomer in the interlamellar region (semi-ordered region). Besides the biotreated PVC presented changes in the C-Cl band at 738 cm1, due to the presence of some PVC conformational isomer. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

The interaction between heparin and Lys49 phospholipase A(2) reveals the natural binding of heparin on the enzyme

We have studied at a molecular level the interaction of heparins on bothropstoxin-1 (BthTx-1), a phospholipase A(2) toxin. The protein was monitored using gel filtration chromatography, dynamic light scattering (DLS), circular dichroism (CD), attenuated total reflectance Fourier transform infrared (ATR-FTIR) and intrinsic tryptophan fluorescence emission (ITFE) spectroscopy. The elution profile of the protein presents a displacement of the protein peak to larger complexes when interacting with higher concentration of heparin. The DLS results shows two R-h at a molar ratio of 1, one to the distribution of the protein and the second for the action of heparin on BthTx-I structures, and a large distribution with the increase of protein. The interaction is accompanied by significant changes in the CD spectra, showing two common features: a decrease in signal at 208 nm (3 and 6 kDa heparins) and an isodichroic point near 226 nm (3 kDa heparin). FTIR spectra indicate that only a few amino acid residues are involved in this interaction. Alterations in the ITFE by binding heparins suggest that the initial binding occurs on the ventral face of BthTx-1. Together, these results add an experimental and structural basis on the action mechanism of the heparins over the phospholipases A(2) and provide a molecular model to elucidate the interaction of the enzyme-heparin complex at a molecular level. (c) 2005 Elsevier B.V. All rights reserved.

Study of the mechanism of action of anoplin, a helical antimicrobial decapeptide with ion channel-like activity, and the role of the amidated C-terminus

Anoplin, an antimicrobial, helical decapeptide from wasp venom, looses its biological activities by mere deamidation of its C-terminus. Secondary structure determination, by circular dichroism spectroscopy in amphipathic environments, and lytic activity in zwitterionic and anionic vesicles showed quite similar results for the amidated and the carboxylated forms of the peptide. The deamidation of the C-terminus introduced a negative charge at an all-positive charged peptide, causing a loss of amphipathicity, as indicated by molecular dynamics simulations in TFE/water mixtures and this subtle modification in a peptide's primary structure disturbed the interaction with bilayers and biological membranes. Although being poorly lytic, the amidated form, but not the carboxylated, presented ion channel-like activity on anionic bilayers with a well-defined conductance step; at approximately the same concentration it showed antimicrobial activity. The pores remain open at trans-negative potentials, preferentially conducting cations, and this situation is equivalent to the interaction of the peptide with bacterial membranes that also maintain a high negative potential inside. Copyright (C) 2007 European Peptide Society and John Wiley & Sons, Ltd.

Effects of Different Swimming Exercise Intensities on Bone Tissue Composition in Mice: A Raman Spectroscopy Study

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Infrared degrees of freedom of Yang-Mills theory in the Schrodinger representation

We set up a new calculational framework for the Yang-Mills vacuum transition amplitude in the Schrodinger representation. After integrating out hard-mode contributions perturbatively and performing a gauge-invariant gradient expansion of the ensuing soft-mode action, a manageable saddle-point expansion for the vacuum overlap can be formulated. In combination with the squeezed approximation to the vacuum wave functional this allows for an essentially analytical treatment of physical amplitudes. Moreover, it leads to the identification of dominant and gauge-invariant classes of gauge field orbits which play the role of gluonic infrared (IR) degrees of freedom. The latter emerge as a diverse set of saddle-point solutions and are represented by unitary matrix fields. We discuss their scale stability, the associated virial theorem and other general properties including topological quantum numbers and action bounds. We then find important saddle-point solutions (most of them solitons) explicitly and examine their physical impact. While some are related to tunneling solutions of the classical Yang-Mills equation, i.e. to instantons and merons, others appear to play unprecedented roles. A remarkable new class of IR degrees of freedom consists of Faddeev-Niemi type link and knot solutions, potentially related to glueballs.

Retention Characteristics of CBTi144 Thin Films Explained by Means of X-Ray Photoemission Spectroscopy

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

Peak Separation by Derivative Spectroscopy Applied to FTIR Analysis of Hydrolized Silica

Reliable spectral analysis is only achieved if the spectrum is thoroughly investigated in regard to all hidden and overlapped peaks. This paper describes the steps undertaken to find and separate such peaks in the range of 3000 to 4000 cm(-1) in the case of three different infrared absorption spectra of the glass surface of hydrolyzed silica optical fibers. Peak finding was done by the analysis of the second and fourth derivatives of the digital data, coupled with the available knowledge of infrared spectroscopy of silica-water interaction in the investigated range. Peak separation was accomplished by curve fitting with four different models. The model with the best fit was described by a sum of pure Gaussian peaks. Shoulder limit and detection limit maps were used to validate the revealed spectral features.