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.

Use of spin label EPR spectra to monitor peptide chain aggregation inside resin beads.

An EPR approach to monitor peptide chain aggregation inside resin beads is introduced. Model low and highly peptide-loaded resins containing an aggregating sequence were labeled with a paramagnetic amino acid derivative and studied with regard to their solvation behavior in different solvent systems. For the first time in the peptide synthesis, EPR spectroscopic has allowed the detection of differentiated levels of peptide chain aggregation as a function of solvent and resin loading. (C) 1997, Elsevier B.V. Ltd. All rights reserved.

Study of the effect of the peptide loading and solvent system in SPPS by HRMAS-NMR

The SPPS methodology has continuously been investigated as a valuable model to monitor the solvation properties of polymeric materials. In this connection, the present work applied HRMAS-NMR spectroscopy to examine the dynamics of an aggregating peptide sequence attached to a resin core with varying peptide loading (up to 80%) and solvent system. Low and high substituted BHAR were used for assembling the VQAAIDYING sequence and some of its minor fragments. The HRMAS-NMR results were in agreement with the swelling of each resin, i.e. there was an improved resolution of resonance peaks in the better solvated conditions. Moreover, the peptide loading and the attached peptide sequence also affected the spectra. Strong peptide chain aggregation was observed mainly in highly peptide loaded resins when solvated in CDCl3. Conversely, due to the better swelling of these highly loaded resins in DMSO, improved NMR spectra were acquired in this polar aprotic solvent, thus enabling the detection of relevant sequence-dependent conformational alterations. The more prominent aggregation was displayed by the VQAAIDYING segment and not by any of its intermediary fragments and these findings were also corroborated by EPR studies of these peptide-resins labelled properly with an amino acid-type spin probe. Copyright (c) 2005 European Peptide Society and John Wiley & Sons, Ltd.

Antibacterial properties of propolis and products containing propolis from Brazil

Crude propolis and commercial products containing propolis, such as ethanolic extracts, tablets, capsules and powders acquired in São Paulo City (Brazil) were analyzed. The resins of the solid products were extracted with ethanol and found to be present at various concentrations, independently of the propolis concentration specified on the label of the commercial products. The in vitro activity of these resins against S aureus, B cereus and B subrilis was also determined. The results showed that the antibacterial activity rather than the propolis concentration itself should be considered for quality control and that some resins are likely to display a species-specific action.

Development of new standard procedures for the evaluation of dental composite abrasive wear

This article discusses the development of a test bench and a methodology for the study of composite resin abrasive wear. To evaluate the operation of the test bench and to compare the proposed methodology with other existing ones, a study was made of the five composites most commonly used by dentists.The one-way ANOVA method and the Tukey test were used to statistically analyze the results by multiple comparisons of the groups of resins tested. Using the proposed methodology, these resins were classified in an increasing order of abrasive wear strength, as follows: Charisma (the lowest abrasive wear strength), Tetric, TPH, Herculite and Z-100 (the highest abrasive wear strength) (P < 0.05). In comparison to other methodologies, the results of the proposed methodology presented the lowest coefficient of variation. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Study of the effects of exposure to ionizing irradiation on the materials used for dental restoration

A quantitative study was made about the effects caused by ionizing irradiation on materials used for dental restoration (amalgams, compound resins and compomere), aiming to alleviate in bearers of head and neck cancer, the possible harmful effects of radiotherapy perceived when the repaired teething is within the radiation field. Research also encourages further studies for new alternative materials to be used in dental repair of patients submitted to radiotherapy for head and neck cancer. Test samples were submitted to a gamma radiation beam coming from a cobalt-therapy source and analyzed according to the X-ray fluorescence technique, comparing the chemical composition of the samples before and after irradiation. Radiation detectors such as an ionization chamber and a Geiger-Muller were used to measure the rate of residual dose. Gamma spectrometry with Nal detectors was also performed on the same samples. Results showed that there was no significant change in the chemical composition and that at post-irradiation, samples did not exhibit radiation emission, that is to say they had not become radioactive.

Effects of processing on the structure of zein/oleic acid films investigated by X-ray diffraction

Zein films plasticized with oleic acid were formed by solution casting, by the stretching of moldable resins, and by blown film extrusion. The effects of the forming process on film structure were investigated by X-ray diffraction. Wide-angle X-ray scattering (WAXS) patterns showed d-spacings at 4.5 and 10 angstrom, which were attributed to the zein alpha-helix backbone and inter-helix packing, respectively. The 4.5.angstrom d-spacing remained stable under processing while the 10 angstrom d-spacing varied with processing treatment. Small-angle X-ray scattering (SAXS) detected a long-range periodicity for the formed films but not for unprocessed zein, which suggests that the forming process-promoted film structure development is possibly aided by oleic acid. The SAXS d-spacing varied among the samples (130-238 angstrom) according to zein origin and film-forming method. X-ray scattering data suggest that the zein molecular structure resists processing but the zein supramolecular arrangements in the formed films are dependent on processing methods.

Spherical particles of phenolic resin treated with iron oxide

This paper describes the preparation and characterization of phenolic resins' thermospheres covered by a magnetic phase of iron oxide. The thermospheres were prepared by allowing phenol and formaldehyde to react under dispersion polymerization conditions and the iron oxide phase was incorporated in situ onto the phenolic resin particles by adding concentrated NH3 to FeCl2 in DMSO. This reaction was conducted at 70 degrees C under nitrogen atmosphere in a controlled temperature vessel, and the modified resin was isolated and dried in vacuo. Both pure and modified resins were characterized by DRX, TG- DTA, and MEV/ EDX. The modified particles were attracted by a magnetic field, indicating the fixation of magnetic iron oxide. No diffraction peaks were observed in DRX analysis; thermal analysis ( DTA) of both pure and modified resins presented exothermic events between 300 and 680 degrees C, and 300 and 570 degrees C, respectively, indicating the microstructure of the resin was modified after the treatment. Thermogravimetric analysis ( TGA) of the pure resin registered a 2.0% residue, compared to 8.0% for the modified resin. These residues correspond to about 7.0% of fixed iron oxide. MEV/ EDX analyses confirm the modification of the resins by the process of fixing iron oxide.

Effect of TiO2 surface modification in Rhodamine B photodegradation

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

Pineapple Leaf Fibers for Composites and Cellulose

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Shear strength evaluation of composite-composite resin associations

Objective: The aim of this study was to investigate the shear strength between distinct associations of different commercial composite resins and their fracture modes.Methods: Nine composite-composite associations (n = 90) were prepared for shear strength evaluation and separated into the following groups: Z/Z (Filtek Z250 UD + Filtek Z250 A2); Z/ D (Filtek Z250 UD + Durafill VS A2); Z/S (Filtek Z250 UD + Filtek Supreme YT); C/C (Charisma OA2 + Charisma A2); C/D (Charisma OA2 + Durafill VS A2); C/S (Charisma OA2 + Filtek Supreme YT); H/H (Herculite XRV B2D + Herculite XRV B2E); H/D (Herculite XRV B2D + Durafill VS A2); H/S (Herculite XRV B2D + Filtek Supreme YT). Shear tests were carried out using universal mechanical test equipment with a load of 200 kgf and speed of 0.5 mm/min. Ultimate shear strength data (MPa) from all tested groups were submitted to analysis of variance (one-way ANOVA) and the Tukey test. The fractured surfaces of the test samples were visually evaluated by binocular stereomicroscope at 20 times magnification. Fractures were classified as either adhesive or cohesive or mixed.Results: The highest ultimate shear strength observed for composite-composite associations was found for the groups: Z/Z, C/S, H/H, H/S, Z/S and C/C. Those associations containing the Durafill resin were weaker than the others.Conclusion: Microparticle RBC associations presented lower shear strength than hybrid and/or nanoparticle RBC associations, once the only significant difference was found when the Durafill resin was involved. (c) 2008 Elsevier Ltd. All rights reserved.

Heterogeneous Fenton reactants: a study of the behavior of iron oxide nanoparticles obtained by the polymeric precursor method

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Protótipos de filtros para água poluida usada para irrigação de hortaliças e frutiferas

Prototypes A (bidin + broken stones + gravel stones + gross sand + activated coal) and B (bidin + broken stones + gravel stones + gross sand) under hydraulic charge of 35 cm presented outlets that, when extrapolated for larger filters, are sufficient to supply small and medium irrigation projects for vegetables and fruits. (bidin = Rhodia polyester for drainage). Under a charge of 35 cm, filtrate of both prototypes presented a reduction of fecal coliforms, being this reduction higher for A prototypes, but, even in this case, the coliform quantities were superior to the legal limit. Under a decrease of the biochemical oxygen demand an increase of the available oxygen rate; pH and hardness did not present significant changes.

Application of propolis to dental sockets and skin wounds.

The purpose of this study was to examine histologically the effects of propolis topical application to dental sockets and skin wounds. After topical application of either a 10% hydro-alcoholic solution of propolis or 10% hydro-alcoholic solution alone, cutaneous wound healing and the socket wound after tooth extraction were examined. The rats were sacrificed at 3, 6, 9, 15 and 21 days after the operation. The specimens were subjected to routine laboratory studies after staining with hematoxylin and eosin. It was concluded that topical application of propolis hydro-alcoholic solution accelerated epithelial repair after tooth extraction but had no effect on socket wound healing.

Influence of different types of non-resorbable suture material on the healing of extraction wounds--a histological study in rats.

The influence of different non-resorbable suture materials on the healing of tooth extraction wounds was examined in 120 adult male albino rats. Nylon gave the best biological results for healing of the mucosa and dental socket. Silk and cotton produced considerable delay of socket healing. Healing was only mildly delayed by polyester suture, with a short moderate inflammatory reaction at the initial stage.