Synthesis of symmetrical 1,3-diynes via homocoupling reaction of n-butyl alkynyltellurides

An ultrasound-assisted synthesis of symmetrical 1,3-diyne compounds with electron-withdrawing or donating substituents is described and illustrated by the palladium-catalyzed homocoupling reaction of n-butyl alkynyltellurides. This procedure offers easy access to 1,3-diynes in very short reaction times, and the products are achieved in good to excellent yields. (C) 2009 Elsevier Ltd. All rights reserved.

Copolymer hydrogels of 2-hydroxyethyl methacrylate with n-butyl methacrylate and cyclohexyl methacrylate: synthesis, characterization and uptake of water

The bulk free radical copolymerizations of 2-hydroxyethyl methacrylate (HEMA) with n-butyl methacrylate (BMA) or cyclohexyl methacrylate (CHMA) were studied over the composition mole fraction interval of 0-1 for HEMA in the monomer feed. The C-13 NMR (125 MHz) spectra of the copolymers were analysed to determine the copolymer composition and the stereochemical configuration of the copolymers. The terminal model reactivity ratios of HEMA and BMA were found to be r(HEMA) = 1.73 and r(BMA) = 0.65 and for HEMA and CHMA, r(HEMA) = 1.26 and r(CHMA) = 0.31. The BMA and CHMA homopolymers were found to be predominantly syndiotactic with isotacticity parameters of theta(BB) = 0.18 and theta(CC) = 0.19, respectively. The copolymers were also found to be predominantly syndiotactic, indicating a strong tendency for racemic additions of the monomers in the formation of the copolymers. The diffusion of water into cylinders of poly(HEMA-co-BMA) and poly(HEMA-co-CHMA) was studied over a range of copolymer compositions and was found to be Fickian. The diffusion coefficients of water at 37 degrees C were determined from swelling measurements and were found to vary from 1.72 x 10(-11) m(2) s(-1) for polyHEMA to 0.97 x 10(-11) m(2) s(-1) for poly(HEMA-co-BMA) having a mole fraction F-HEMA = 0.80 and to 0.91 x 10(-11) m(2) s(-1) for a poly(HEMA-co-CHMA) also having F-HEMA = 0.80. The mass of water absorbed at equilibrium relative to the mass of dry polymer varied from 58.8 for polyHEMA to 27.2% for poly(HEMA-co-BMA) having F-HEMA = 0.85 and to 21.3% for poly(HEMA-co-CHMA) having F-HEMA = 0.80. (C) 1999 Elsevier Science Ltd. All rights reserved.

Increased Vascular Permeability, Angiogenesis and Wound Healing Induced by the Serum of Natural Latex of the Rubber Tree Hevea brasiliensis

Increases in vascular permeability and angiogenesis are crucial events to wound repair, tumoral growth and revascularization of tissues submitted to ischemia. An increased vascular permeability allows a variety of cytokines and growth factors to reach the damaged tissue. Nevertheless, the angiogenesis supply tissues with a wide variety of nutrients and is also important to metabolites clearance. It has been suggested that the natural latex from Hevea brasiliensis showed wound healing properties and angiogenic activity. Thus, the purpose of this work was to characterize its angiogenic activity and its effects on vascular permeability and wound healing. The serum fraction of the latex was separated from the rubber with reduction of the pH. The activity of the dialyzed serum fraction on the vascular permeability injected in subcutaneous tissue was assayed according Mile`s method. The angiogenic activity was determined using a chick embryo chorioallantoic membrane assay and its effects on the wound-healing process was determined by the rabbit ear dermal ulcer model. The serum fraction showed evident angiogenic effect and it was effective in enhancing vascular permeability. In dermal ulcers, this material significantly accelerated wound healing. Moreover, the serum fraction boiled and treated with proteases lost these activities. These results are in accordance with the enhancement of wound healing observed in clinical trials carried out with a biomembrane prepared with the same natural latex. Copyright (C) 2009 John Wiley & Sons, Ltd.

Temporal evolution of epithelial, vascular and interstitial lung injury in an experimental model of idiopathic pulmonary fibrosis induced by butyl-hydroxytoluene

This study was undertaken to test whether the structural remodelling of pulmonary parenchyma can be sequentially altered in a model and method that demonstrate the progression of the disease and result in remodelling within the lungs that is typical of idiopathic pulmonary fibrosis. Three groups of mice were studied: (i) animals that received 3-5-di-tert-butyl-4-hydroxytoluene (BHT) and were killed after 2 weeks (early BHT = 9); (ii) animals that received BHT and were killed after 4 weeks (late BHT = 11); (iii) animals that received corn oil solution (control = 10). The mice were placed in a ventilated Plexiglas chamber with a mixture of pure humidified oxygen and compressed air. Lung histological sections underwent haematoxylin-eosin, immunohistochemistry (epithelial, endothelial and immune cells) and specific staining (collagen/elastic fibres) methods for morphometric analysis. When compared with the control group, early BHT and late BHT groups showed significant decrease of type II pneumocytes, lower vascular density in both and higher endothelial activity. CD4 was increased in late BHT compared with early and control groups, while CD8, macrophage and neutrophil cells were more prominent only in early BHT. The collagenous fibre density were significantly higher only in late BHT, whereas elastic fibre content in late BHT was lower than that in control group. We conclude that the BHT experimental model is pathologically very similar to human usual interstitial pneumonia. This feature is important in the identification of animal models of idiopathic pulmonary fibrosis that can accurately reflect the pathogenesis and progression of the human disease.

Reproductive development and function of female rats exposed to di-eta-butyl-phthalate (DBP) in utero and during lactation

Phthalates are environmental contaminants used in the production of plastics, cosmetics and medical devices. Studies on the effects of phthalates on female reproductive health are particularly sparse and mostly restricted to high-dose exposure in rats. In the present study, pregnant rats were treated with 100 mg/kg-d of di-eta-butyl-phthalate (DBP) or only the vehicle (control group), from GD 12 to GD 20 for evaluation of reproductive outcomes and fetal gonads analysis (F0), and from GD 12 to PND 21 to evaluate reproductive development and function on F1 female offspring. Results showed that all parameters were comparable between groups, although there was a significant increase in the fetal weight after DBP exposure. However, the body weight at birth was normal. Based on these data we can conclude that, in these experimental conditions, DBP did not disturb the reproductive development or function of female rats. (C) 2009 Elsevier Inc. All rights reserved.

Long-term effects of developmental exposure to di-n-butyl-phthalate (DBP) on rat prostate: Proliferative and inflammatory disorders and a possible role of androgens

In the present study we evaluated the toxic effects on the male adult rat prostate of DBP exposure during fetal and lactational periods, because although many studies have addressed the influence of phthalates on the male reproductive system, only a few have discussed their possible effects on prostate development. Pregnant females were distributed into two experimental groups: Control (C) and Treated (T). The females of the T group received DBP (100 mg/kg, by gavage) from gestation day 12 to postnatal day 21, while C rats received the vehicle (corn oil). In adulthood (90 days old), the animals were euthanized. The serum and testicular testosterone levels were measured. Ventral prostate was removed and weighed. Distal segment fragments of the ventral prostate were fixed and processed for histochemistry and immunohistochemistry to detect androgen receptor (AR) and Ki67 antigens. Protein extraction from ventral prostate fragments was performed for AR immunoblotting and Gelatin zymography for MMP-2 and MMP-9 (MMP, metalloproteinase). Stereological and histopathological analyses were also performed. Serum and testicular testosterone levels and prostate weight were comparable between groups. In the T group the relative proportions (%) of epithelial (C=32.86; T=42.04*) and stromal (C=21.61; T=27.88*) compartments were increased, while the luminal compartment was decreased (C=45.54; T=30.08*), *p < 0.05. In T, disseminated inflammatory infiltrate in the stroma, associated or not with epithelial dysplasia and PIN (Prostatic Intraepithelial Neoplasia), was observed. Increases in AR expression, proliferation index and metalloproteinase 9 (MMP-9) activity were noted in T animals. In some T animals, collagen fibrils accumulated adjacent to the epithelium. As far as we are aware, this is the first report in the literature showing that phthalates could play a role in proliferative and inflammatory disorders of the rat prostate. (C) 2009 Elsevier Ireland Ltd. All rights reserved.

Asphalt rubber mixtures in Portugal: fatigue resistance

This paper presents a study concerning the fatigue behaviour of asphalt mixtures with bitumen modified with high content of crumb rubber used in Portugal. For assessing the fatigue behaviour of this type of mixtures, four asphalt mixtures with high content of crumb rubber were used: two field bituminous mixtures – an open-graded and a gap-graded – both with granite aggregates; and two laboratory manufactured bituminous mixtures – an open-graded mixture with granite aggregates and a gap-graded mixture with crushed gravel aggregates. Since this type of mixtures are mainly applied in wearing courses, the effect of ageing in the fatigue behaviour of one of the studied asphalt rubber mixtures was also assessed through laboratory testing. The paper presents the main results achieved so far concerning the fatigue resistance and it could be concluded that all the materials have exhibited a good behaviour, in agreement with others previous studies. In the case of the aged gap-graded material, it was observed a slight reduction on the fatigue life comparatively to the un-aged one.

Toxicological Assessment of Coated versus Uncoated Rubber Granulates Obtained from Used Tires for Use in Sport Facilities

Reuse of tire crumb in sport facilities is currently a very cost-effective waste management measure. Considering that incorporation of the waste materials in artificial turf would be facilitated if the rubber materials were already colored green, coatings were specifically developed for this purpose. This paper presents an experimental toxicological and environmental assessment aimed at comparing the obtained emissions to the environment in terms of polycyclic aromatic hydrocarbons (PAHs), heavy metals, and ecotoxicity for coated and noncoated rubber granulates. This study is a comprehensive evaluation of the major potential critical factors related with the release of all of these classes of pollutants because previous studies were not systematically performed. It was concluded that between the two types of coatings tested, one is particularly effective in reducing emissions to the environment, simultaneously meeting the requirements of adherence and color stability.

Enthalpies of Solution of 1-Butyl-3-methylimidazolium Tetrafluoroborate in 15 Solvents at 298.15 K

Enthalpies of solution of 1-butyl-3-methylimidazolium tetra fluoroborate, [BMIm]BF4, are reported at 298.15 K in a set of 15 hydrogen bond donor and hydrogen bond acceptor solvents, chosen by their diversity, namely, water, methanol, ethanol, 1,2-ethanediol, 2-choroethanol, 2-methoxyethanol, formamide, propylene carbonate, nitromethane, acetonitrile, dimethyl sulfoxide, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, and aniline. These values are shown to be largely independent of [BMIm]BF4 concentration. The obtained enthalpies of solution vary from very endothermic to quite exothermic, thus showing a very high sensitivity of the enthalpies of solution of [BMIm]BF4 to solvent properties. Solvent effects on the solution process of this IL are analyzed by a quantitative structure-property relationship methodology, using the TAKA equation and a modified equation, which significantly improves the model's predictive ability. The observed differences in the enthalpies of solution are rationalized in terms of the solvent properties found to be relevant, that is, pi* and E-T(N).

Design of a new test chamber for evaluation of the toxicity of rubber infill

A test chamber was projected and built (according to ISO 16000-9 Standard) to simulate atmospheric conditions experienced by rubber infill (when applied in synthetic turf pitches) and measure accurately the airborne emissions of pollutants such as dusts and volatile organic compounds (VOC), as well as pollutants present in leachates. It should be pointed out that standard ISO 16000-9 is only concerned with the determination of the emission of VOC from building products and furnishing (not specific of synthetic turf materials), whereas other standards are concerned with the emission of leachates only. This procedure is to be considered as a technical option to the lysimeter "global turf system evaluation" when the rubber infill alone is to be evaluated. The advantage of the proposed option considering this "test chamber" is its simplicity and economy. This test chamber is actually installed and being used for tests in LAIST.

Toxicological Assessment of Coated versus Uncoated Rubber Granulates Obtained from Used Tires for Use in Sport Facilities

Reuse of tire crumb in sport facilities is currently a very cost-effective waste management measure. Considering that incorporation of the waste materials in artificial turf would be facilitated if the rubber materials were already colored green, coatings were specifically developed for this purpose. This paper presents an experimental toxicological and environmental assessment aimed at comparing the obtained emissions to the environment in terms of polycyclic aromatic hydrocarbons (PAHs), heavy metals, and ecotoxicity for coated and noncoated rubber granulates. This study is a comprehensive evaluation of the major potential critical factors related with the release of all of these classes of pollutants because previous studies were not systematically performed. It was concluded that between the two types of coatings tested, one is particularly effective in reducing emissions to the environment, simultaneously meeting the requirements of adherence and color stability.

RubBer Contact Dermatitis in patients attended at Walter Cantídio Hospital, Federal University of Ceará, Brasil

Nowadays 70% of the world's rubber supply is synthesized artificially. The process involved in its manufacture is vulcanization which requires many chemical substances for speeding the process, as antioxidants to prevent deterioration of rubber, or others. These substances may constitute important sensitizers and thus be responsible for dermatological diseases like contact dermatitis. The objective of this study is to search for the main sensitizers among these rubber chemicals in a population mostly composed by women of a tropical country and compare the results with the ones obtained from previous studies which tested populations mainly composed by men and on different climates.

Estudo da Fiabilidade de Rubber Tyred Gantry

Dissertação para obtenção do Grau de Mestre em Engenharia e Gestão Industrial

Effectiveness of house dust mite acaricide tri-n-butyl tin maleate on carpets, fabrics and mattress foam: a standardization of methodology

The aim of this study was to determine the effectiveness of the acaricide tri-n-butyl tin maleate, industrially applied to samples of carpets, mattress foam, and fabrics used for furniture upholstery, soft toys and shoe uppers. Approximately 100 adult house dust mites of the species Dermatophagoides pteronyssinus were inoculated into a Petri dish containing the sample (a piece of carpet, mattress foam, or fabric), treated with the acaricide, randomly collected. Mite-maintenance culture medium was added on top of each sample. After one, two, three, seven and 30 days of incubation at 25 ºC and 75% relative humidity, each dish was examined using a 40X stereoscopic microscope (40X). One hundred percent acaricide effectiveness was obtained in treated materials by the end of the 30th-day postinoculation period, under optimal conditions for mite maintenance.