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.

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.

Polygala paniculata: um recurso de salicilato de metila produzido por cultura de tecidos vegetais

O estabelecimento de cultura in vitro de Polygala paniculata L. permitiu a propagação rápida de matéria-prima vegetal sob condições assépticas e padronizadas. As plantas in vitro foram submetidas à extração e destilação simultâneas (EDS) e a composição química do óleo essencial foi analisada por CG/DIC e CG/EM. Foram avaliados os efeitos de BAP (6-benzilaminopurina) sobre o desenvolvimento in vitro e produção de voláteis em P. paniculata. A principal característica do óleo essencial consistiu na presença marcante de salicilato de metila. Plantas cultivadas em meio controle MS (Murashige & Skoog) produziram mais do que 80% de salicilato, enquanto o uso de BAP, reduziu a produção de salicilato de metila a 71% e 21% para as concentrações de 2 e 4 mg L-1, respectivamente. A cultura de tecidos de P. paniculata pode ser indicada como fonte de salicilato de metila.

Síntese de poli(p-xililenos)

Poly(p-xylylenes), PPX, are a class of high performance insulating materials with many applications in the electronic component industry. We review herewith the most important synthetic routes to these polymers, described in the literature, since 1904.

Determinação de baixas concentrações de cobre em águas naturais por espectrofotometria de absorção atômica em chama usando um sistema SIA com uma coluna de poli(etilenimina)

This paper describes a sequential injection analysis (SIA) set-up coupled to a flame atomic absorption spectrometer (FAAS) to accomplish the determination of low concentrations of copper in drinking waters. Copper is first retained under neutral media in an on-line 29x1.6 mm column filled with poly(ethylenimine) immobilised on silica gel. The retained analyte is then eluted by flowing through the column 250 mL of a nitric acid solution. The selection of 3.85 ml of sample enabled to obtain a detection limit of 0.27 mug/L and a sampling rate of about 24 samples/h. There was a good agrement between the results of 12 samples furnished by the proposed procedure and by electrothermal atomic absorption spectrometry. Repeatability assessment gave a relative standard deviation of 1.3 % after ten replicate analysis of a sample containing about 70 mug/L in copper..

Cristalização e taxa crítica de resfriamento para vitrificação do poli(sebacato de decametileno)

We synthesized Poly(decamethylene sebacate) - P10MS - and studied its overall crystallization rates in a range of temperatures using Differential Scanning Calorimetry in isothermal conditions, which enabled us to identify the crystallization mechanism by means of the Johnson-Mehl-Avrami-Kolmogorov equation. The critical cooling rate (Rc) to vitrify the P10MS was determined using a non-isothermal method proposed by Barandiarán & Colmenero (BC). The value of Rc is around 50-250 K/s, which confirms the experimentally observed difficulty to vitrify this polymer.

Estratégias de cultivo para produção dos plásticos biodegradáveis poli(3-Hidroxibutirato) e poli(3-hidroxibutirato-co-3-hidroxivalerato) por bactérias

Polyhydroxyalkanoates (PHAs) are carbon and energy storage materials that are accumulated as intracellular granules in a variety of microorganisms during unbalanced growth. PHAs have drawn attention due to their properties similar to conventional plastics and complete biodegradability. They can be used for food and cosmetics packaging, and in medicine and agriculture. However, their applicability is reduced because of their high production cost compared to conventional plastics. An overview on production strategies of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) aiming at reducing the production costs is presented.

Preparação e caracterização óptica de filmes de poli(estireno sulfonados) dopados com neodímio

In this work we describe the processing of poly(styrene sulphonate) films (PSS) doped with neodymium (Nd). Optical density measurements in the UV-Vis-NIR region show the typical bands observed for neodymium chloride (NdCl3) in solution. In the case of films, the intensity ratio between the peaks at 800 nm (4I9/2 -> 4F5/2 + ²H7/2) and 580 nm (4I9/2 -> 4G5/2 + ²G7/2) is equal to 0.83. Infrared spectra present an enhancement in the absorption region of aromatic rings. Site selective luminescence spectroscopy shows that the incorporation of Nd introduces a hipsochromic shift and a line shape definition in UV luminescence compared to PSS film, decreasing the interaction between aromatic groups. In addition, the film exhibits an intense radiative transition at 1061 nm (4F3/2->4I11/2), comparable to the one present in crystalline materials doped with Nd.

Novos sorventes baseados em poli (metiloctilsiloxano) sobre sílica para uso em extração em fase sólida

This paper presents an easy and practical procedure to obtain silica-based C-8 type sorbents for use in solid-phase extraction. The materials are prepared by depositing poly(methyloctylsiloxane), PMOS, on the silica support. Two different treatments for immobilization were used: thermal treatment or gamma irradiation. Suitable recoveries were obtained after pre-concentration of dilute solutions, at the ng/L level, of a mixture of pesticides, indicating the good performance of the materials.

Influência da espessura nas propriedades de absorção e emissão e na morfologia de filmes automontados de poli(p-fenileno vinileno)

In this report, we studied the thickness effect on the optical and morphological properties of self-assembled (SA) poly(p-phenylenevinylene) (PPV) films, wich were processed with 5 and 75 layers from a PPV precursor polymer and dodecylbenzenesulfonate, and then, thermally converted at 230 °C. The increase of the film thickness yielded more intense peaks in the vibrational spectral range. The electron-phonon coupling was quantified by the Huang - Rhys factor, that shows the effects on the polymer chain mobility in the interface substrate/polymer. A strong emission anisotropy r=0.57 was observed for the film with 5 layers of thickness decreasing to 0.34 for the film with 75 layers. Finally, the surface topology of the films was measured using Atomic Force Microscopy.

Controle da biossíntese de poli-hidroxialcanoatos bacterianos através do fluxo de substratos

Manipulation of the flux of substrates was utilized to control the amount of 3-hydroxyvalerate and 3-hydroxy-4-pentenoate produced by Burkohlderia sp. The 3HV production rate was directly proportional to the propionic acid uptake rate with the last one completely directed to 3HV biosynthesis. The 3HPE production rate was inversely proportional to the sucrose uptake rate probably due to operation of the glyoxylate cycle.

Nanocompósitos eletroativos de poli-o-metoxianilina e polissacarídeos naturais

In this work we take advantage of the polyelectrolyte character of some Brazilian native gums to fabricate electrically conductive, nanostructured films. The gums Sterculia urens, (caraia), Sterculia striata (chicha) or Anadenanthera macrocarpa Benth were assembled in conjunction with poly(o-methoxyaniline) (POMA) in the form of layered nanostructured films using the layer-by-layer (LbL) technique. All the LbL films displayed a well-defined electroactivity, as confirmed via cyclic voltammetry. In comparison to POMA LbL films fabricated with conventional polyelectrolytes (viz. poly(vinyl sulfonic acid)-PVS), the presence of the gums in the LbL films increased remarkably the electrochemical stability of the films.

Produção biotecnológica de poli-hidroxialcanoatos para a geração de polímeros biodegradáveis no Brasil

In recent years, several studies have been developed in Brazil to produce biodegradable materials. A particular family of bacterial polymers, the polyhydroxyalkanoates (PHA), has received special attention. PHAs are thermoplastic, biodegradable, biocompatible, are synthesised from renewable resources and can substitute petrochemical plastics in some applications. Different aspects have been focused to increase productivity and to reduce the cost of PHA production: bacterial improvement, use of industrial by-products as raw material, bioreactor design, process operation strategies, downstream process, mathematical modelling, polymer characterisation, application and biodegradability of blends. A production process was transferred to industry and studies to produce new PHA by controlling monomer composition are in progress. All these aspects are presented in this review.

Síntese e caracterização de dispersões aquosas de poliuretanos à base de copolímeros em bloco de poli(glicol etilênico) e poli(glicol propilênico)

Non-polluting polyurethane aqueous dispersions, with 40% of solids content, were synthesized based on block copolymers of poly(ethylene glycol) and poly(propylene glycol) (PEG-b-PPG), with PEG hydrophilic segments content of 7 and 25%, poly(propylene glycol) (PPG), dimethylolpropionic acid (DMPA), isophorone diisocyanate (IPDI), and hydrazine. Different formulations were synthesized by varying the equivalent-grams ratios between isocyanate and hydroxyl groups (NCO/OH) and PPG and (PEG-b-PPG). The presence of high amounts of PEG in the formulations provoked the formation of gels. Average particle size and viscosity of the dispersions were determined. Mechanical properties and water absorption resistance of cast films were evaluated.

Preparação e caracterização de blendas de quitosana/poli(álcool vinílico) reticuladas quimicamente com glutaraldeído para aplicação em engenharia de tecido

In this study, novel Chitosan/PVA based films were chemically crosslinked by glutaraldehyde, under pH=(4,00 ±0,05), in order to achieve structures tailored for wound tissue engineering applications. Both precursors and developed films were characterized by FTIR, SEM and XRD in order to determine the presence of chemicals groups and nanostructural order, respectively. The results have shown that the glutaraldehyde crosslinking have altered the crystallinity of pure chitosan and the increase on the C=N bands and simultaneous decrease on NH2 bands suggested that Chitosan/GA crosslinking has preference to occur in carbon-2 of the saccharide ring by the Schiff's base reaction. Also, FTIR spectroscopy clearly showed that crosslinking has also taken place with blends of PVA and chitosan. The mechanical properties presented high degree dependence with on the increase of the content of chitosan and glutaraldehyde. The results have indicated that, by controlling the ratio [PVA]/[chitosan] in the blends and the extent of chemical crosslinking, it was possible to tailor the hybrid network produced aiming to obtain properties of interest for the specific application.