Irradiação de polímeros com feixe de elétrons: caracterização de íons positivos através da técnica de tempo-de-vôo

With the aim of studying the interaction of fast electrons with solid surfaces we have developed an experimental set-up based on electron stimulated desorption (ESD) coupled to time-of-flight (TOF) mass spectrometry. Poly(methyl methacrylate) and poly(vynil chloride) samples have been irradiated by a pulsed electron beam of 1.2 keV and 0.18 µs FWHM. The results show that H+ is the main ionic species to desorb after electron bombardment. In addition, other ionic fragments were also observed and assigned. These results show the potentiality of this technique in the study of ESD of polymers.

Síntese de fotoprotetores e sua imobilização em poli(metacrilato de metilo): um projeto integrado de química orgânica, química de polímeros e fotoquímica

Dibenzalacetone and other aldol condensation products are known sunscreens commonly used in cosmetics. This type of compounds can easily be prepared in an Organic Chemistry Lab by reaction of aldehydes with ketones in basic medium. These compounds can be incorporated in poly(methyl methacrylate) and used as UV light absorbers, for example in sunglasses. This project has the advantage of using inexpensive reagents which are readily available in Chemistry Laboratories. This experiment can also be a base starting point for discussions of organic, polymer and photochemistry topics.

Biomechanical and histological evaluation of hydrogel implants in articular cartilage

We evaluated the mechanical behavior of the repaired surfaces of defective articular cartilage in the intercondylar region of the rat femur after a hydrogel graft implant. The results were compared to those for the adjacent normal articular cartilage and for control surfaces where the defects remained empty. Hydrogel synthesized by blending poly(2-hydroxyethyl methacrylate) and poly(methyl methacrylate-co-acrylic acid) was implanted in male Wistar rats. The animals were divided into five groups with postoperative follow-up periods of 3, 5, 8, 12 and 16 weeks. Indentation tests were performed on the neoformed surfaces in the knee joint (with or without a hydrogel implant) and on adjacent articular cartilage in order to assess the mechanical properties of the newly formed surface. Kruskal-Wallis analysis indicated that the mechanical behavior of the neoformed surfaces was significantly different from that of normal cartilage. Histological analysis of the repaired defects showed that the hydrogel implant filled the defect with no signs of inflammation as it was well anchored to the surrounding tissues, resulting in a newly formed articular surface. In the case of empty control defects, osseous tissue grew inside the defects and fibrous tissue formed on the articular surface of the defects. The repaired surface of the hydrogel implant was more compliant than normal articular cartilage throughout the 16 weeks following the operation, whereas the fibrous tissue that formed postoperatively over the empty defect was stiffer than normal articular cartilage after 5 weeks. This stiffness started to decrease 16 weeks after the operation, probably due to tissue degeneration. Thus, from the biomechanical and histological point of view, the hydrogel implant improved the articular surface repair.

Excitação eletrônica das moléculas de metacrilato de metila e estireno na região do ultravioleta de vácuo

Angle-resolved electron energy-loss spectra have been measured for the methyl methacrylate (MMA) and styrene molecules in the 0 - 50 eV energy range. The spectra have been obtained at 1 keV incident energy, with an energy resolution of 0.8 eV and covering an angular range of 2.0 to 7.0 degrees. Within our knowledge, this is the first gas-phase excitation spectrum for MMA and styrene in this energy range. The spectra of MMA at small scattering angles are dominated by an intense peak at 6.7 eV followed by a broad band centered at about 16 eV. In the case of styrene, six bands can be observed in the spectra. Based on the angular behaviour of the excitation spectra of these molecules, the low-lying peaks observed are considered to be associated predominantly with dipole-allowed processes. In both cases, new bands can be observed for excitation energies greater than 20 eV. This could be associated with dipole-forbidden transitions to shake-up and doubly-excited states.

Thermal behaviour of TEGMMA copolymers obtained by photopolymerization using iron complexes

Copolymers of methyl methacrylate (MMA) and triethyleneglycol dimethacrylate (TEGDMA) obtained by photoinitiated polymerization using Fe(III) complexes were submitted to thermogravimetry (TGA) under dynamic air atmosphere and N2, and differential scanning calorimetric analysis (DSC). Thermal events were observed only between 90 - 110 ºC. Glass transitions were observed at ca. 100 ºC, followed by an exothermic peak at 170 ºC. The exothermic peak was assigned to a thermal curing process due to the presence of unreacted vinyl groups of the monomers. DSC revealed to be a useful tool to evaluate the curing completeness in this kind of material, using small amounts of sample in relatively short time.

Poly(ethylene-co-methyl acrylate)/poly(caprolactone) triol blends for drug delivery systems: characterization and drug release

Poly(ethylene-co-methyl acrylate) (EMA) and poly (caprolactone) triol (PCL-T) blends, a biodegradable aliphatic polyester with low molecular weight and moderate water solubility containing diltiazem hydrochloride (DZ) were studied in terms of the thermal and morphological properties, and drug release mechanism. An increase in the PCL-T content in the EMA/PCL-T/DZ films decreased the degree of DZ crystallinity. Drug release from these films is temperature-dependent, and it is possible to modify the drug release rate by adjusting the EMA/PCL-T composition of the blends. The mechanism of drug release is governed by PCL-T melting and PCL-T leaching from EMA matrix.

Monomer conversion of composite dental resins photoactivated by a halogen lamp and a LED: a FT-Raman spectroscopy study

Eighteen circular blocks of resins cured either by a LED or a halogen lamp (20, 40 and 60 s), had their top (T) and bottom (B) surfaces studied using a FT-Raman spectrometer. Systematic changes in the intensity of the methacrylate C=C stretching mode at 1638 cm-1 as a function of exposure duration were observed. The calculated degree of conversion (DC) ranged from 45.0% (B) to 52.0% (T) and from 49.0% (B) to 55.0% (T) for the LED and halogen lamp, respectively. LED and halogen light produced similar DC values with 40 and 60 s of irradiation.

Mucosal leishmaniasis ("espundia") responsive to low dose of N-methyl glucamine (Glucantime ®) in Rio de Janeiro, Brazil

Response to treatment with antimonial drugs varies considerably depending on the parasite strain involved, immune status of the patient and clinical form of the disease. Therapeutic regimens with this first line drug have been frequently modified both, in dose and duration of therapy. A regimen of 20 mg/kg/day of pentavalent antimony (Sb5+) during four weeks without an upper limit on the daily dose is currently recommended for mucosal disease ("espundia"). Side-effects with this dose are more marked in elderly patients, more commonly affected by this form of leishmaniasis. According to our experience, leishmaniasis in Rio de Janeiro responds well to antimony and, in cutaneous disease, high cure rates are obtained with 5 mg/kg/day of Sb5+ during 30 to 45-days. In this study a high rate of cure (91.4%) employing this dose was achieved in 36 patients with mild disease in this same geographic region. Side-effects were reduced and no antimony refractoriness was noted with subsequent use of larger dose in patients that failed to respond to initial schedule.

In vitro antifungal activity of fatty acid methyl esters of the seeds of Annona cornifolia A.St.-Hil. (Annonaceae) against pathogenic fungus Paracoccidioides brasiliensis

INTRODUCTION: Fatty acids are abundant in vegetable oils. They are known to have antibacterial and antifungal properties. METHODS: Antifungal susceptibility was evaluated by broth microdilution assay following CLSI (formerly the NCCLS) guidelines against 16 fungal strains of clinical interest. RESULTS: In this work, fatty acid methyl esters (FAME) was able to inhibit 12 clinical strains of the pathogenic fungus Paracoccidioides brasiliensis and were also active in the bioautographic assay against Cladosporium sphaerospermum. CONCLUSIONS: FAME was a more potent antifungal than trimethoprim-sulfamethoxazole against P. brasiliensis under the experimental conditions tested.

Larvicidal activity of oils, fatty acids, and methyl esters from ripe and unripe fruit of Solanum lycocarpum (Solanaceae) against the vector Culex quinquefasciatus (Diptera: Culicidae)

ABSTRACTINTRODUCTION:The larvicidal activity of oils, fatty acids, and methyl esters of Solanum lycocarpum fruit against Culex quinquefasciatus is unknown.METHODS:The larvicidal activity of samples of ripe and unripe fruit from S. lycocarpum was evaluated against third and fourth instar larvae of C. quinquefasciatus .RESULTS:The oils, fatty acids, and methyl esters of S. lycocarpum showed the greatest larvicidal effect (57.1-95.0%) at a concentration of 100mg/L (LC 50values between 0.70 and 27.54mg/L).CONCLUSIONS:Solanum lycocarpum fruit may be a good source of new natural products with larvicidal activity.

The chemistry of Brazilian leguminosae. LXI. (+)-Methyl Vouacapenate from Vouacapoua pallidior

Thz wood of Vouacapoua pallidior (Leguminosae-Caesalpinioideae) Contains (+)-methyl vouacapenate.

Endothelium-dependent relaxation in response to poly-L-arginine in canine coronary arteries: implications about hyperpolarization as a mechanism of vasodilatation

OBJECTIVE: To study the mechanism by which poly-L-arginine mediates endothelium-dependent relaxation. METHODS: Vascular segments with and without endothelium were suspended in organ chambers filled with control solution maintained at 37ºC and bubbled with 95% O2 / 5% CO2. Used drugs: indomethacin, acetycholine, EGTA, glybenclamide, ouabain, poly-L-arginine, methylene blue, N G-nitro-L-arginine, and verapamil and N G-monomethyl-L-arginine. Prostaglandin F2á and potassium chloride were used to contract the vascular rings. RESULTS: Poly-L-arginine (10-11 to 10-7 M) induced concentration-dependent relaxation in coronary artery segments with endothelium. The relaxation to poly-L-arginine was attenuated by ouabain, but was unaffected by glybenclamide. L-NOARG and oxyhemoglobin caused attenuation, but did not abolish this relaxation. Also, the relaxations was unaffected by methylene blue, verapamil, or the presence of a calcium-free bathing medium. The endothelium-dependent to poly-L-arginine relaxation was abolished only in vessels contracted with potassium chloride (40 mM) in the presence of L-NOARG and indomethacin. CONCLUSION: These experiments indicate that poly-L-arginine induces relaxation independent of nitric oxide.

Molecular Modeling Approaches for Determining Gene Function: application to a Putative Poly-A Binding Protein from Leishmania amazonensis (LaPABP)

The great expansion in the number of genome sequencing projects has revealed the importance of computational methods to speed up the characterization of unknown genes. These studies have been improved by the use of three dimensional information from the predicted proteins generated by molecular modeling techniques. In this work, we disclose the structure-function relationship of a gene product from Leishmania amazonensis by applying molecular modeling and bioinformatics techniques. The analyzed sequence encodes a 159 aminoacids polypeptide (estimated 18 kDa) and was denoted LaPABP for its high homology with poly-A binding proteins from trypanosomatids. The domain structure, clustering analysis and a three dimensional model of LaPABP, basically obtained by homology modeling on the structure of the human poly-A binding protein, are described. Based on the analysis of the electrostatic potential mapped on the model's surface and conservation of intramolecular contacts responsible for folding stabilization we hypothesize that this protein may have less avidity to RNA than it's L. major counterpart but still account for a significant functional activity in the parasite. The model obtained will help in the design of mutagenesis experiments aimed to elucidate the mechanism of gene expression in trypanosomatids and serve as a starting point for its exploration as a potential source of targets for a rational chemotherapy.

The pathogenesis of diabetic complications: the role of DNA injury and poly(ADP-ribose) polymerase activation in peroxynitrite-mediated cytotoxicity

Recent work has demonstrated that hyperglycemia-induced overproduction of superoxide by the mitochondrial electron-transport chain triggers several pathways of injury [(protein kinase C (PKC), hexosamine and polyol pathway fluxes, advanced glycation end product formation (AGE)] involved in the pathogenesis of diabetic complications by inhibiting glyceraldehyde-3-phosphate dehydrogenase (GAPDH) activity. Increased oxidative and nitrosative stress activates the nuclear enzyme, poly(ADP-ribose) polymerase-1 (PARP). PARP activation, on one hand, depletes its substrate, NAD+, slowing the rate of glycolysis, electron transport and ATP formation. On the other hand, PARP activation results in inhibition of GAPDH by poly-ADP-ribosylation. These processes result in acute endothelial dysfunction in diabetic blood vessels, which importantly contributes to the development of various diabetic complications. Accordingly, hyperglycemia-induced activation of PKC and AGE formation are prevented by inhibition of PARP activity. Furthermore, inhibition of PARP protects against diabetic cardiovascular dysfunction in rodent models of cardiomyopathy, nephropathy, neuropathy, and retinopathy. PARP activation is also present in microvasculature of human diabetic subjects. The present review focuses on the role of PARP in diabetic complications and emphasizes the therapeutic potential of PARP inhibition in the prevention or reversal of diabetic complications.