Hidrólise seletiva de carboxiamidas de resíduos de asparagina e glutamina em colágeno: preparação e caracterização de matrizes aniônicas para uso como biomateriais

This work describes the selective hydrolysis of carboxyamide groups of asparagine and glutamine of collagen matrices for the preparation of negatively charged collagen biomaterials. The reaction was performed in the presence of chloride and sulfate salts of alkaline and alkaline earth metals in aqueous dimethylsulfoxide solution and, selectively hydrolysis of carboxyamide groups of collagen matrices was promoted without cleavage of the peptide bond. The result is a new collagen material with controlled increase in negative charge content. Although triple helix secondary structure of tropocollagen was preserved, significative changes in thermal stabilities were observed in association with a new pattern of tropocollagen macromolecular association, particularly in respect microfibril assembly, thus providing at physiological pH a new type of collagen structure for biomaterial preparation, characterized by different charge and structural contents .

Hidróxidos duplos lamelares: síntese, estrutura, propriedades e aplicações

The layered double hydroxides, known as anionic clays and represented by the general formula [M2+1-x M3+x (OH) 2]x+ Am-x/m·nH 2O, are a group of materials which are of much interest currently. They present a variety of potential applications as adsorbents, catalysts and catalyst support, ion-exchangers, antacids and as a polymer stabilizer. It is possible to obtain a broad variety of layered double hydroxides (LDHs), depending on the identity and ratio of the cations M2+ and M3+, as well as the interlamelar anion. The aim of this review is to give out some information about this class of materials, concerning to the synthesis, characterization, properties and applications.

Determinações multi-elementares de metais, Sulfato e Cloreto em amostras de águas por espectrometria de massas com fonte de plasma (ICP-MS)

The multi-element determination of Al, Cr, Mn, Ni, Cu, Zn, Cd, Ba, Pb, SO4= and Cl- in riverine water samples was accomplished by inductively coupled plasma mass spectrometry (ICP-MS). The sample passed through a column containing the anionic resin AG1-X8 and the metals were determined directly. The retained anionic species were eluted and SO4= and Cl- were determined at m/z 48 and 35 correspondent to the ions SO+ and Cl+ formed at the plasma. Accuracy for metals was assessed by analysing the certified reference TM-26 (National Water Research Institute of Canada). Results for SO4= and Cl- were in agreement with those obtained by turbidimetry and spectrophotometry. LOD's of 0.1 µg l-1 for Cd, Ba and Pb; 0.2 µg l-1 for Al, Mn and Cu; 0.5 µg l-1 for Cr; 0.9 for Zn; 2.0 µg l-1for Ni , 60 µg l-1 for S and 200 µg l-1 Cl were attained.

Organo-gel de heptano: diagrama de fases e aplicações sintéticas

The phase diagram formation of microemulsion-based gels composed of an anionic surfactant aerosol-OT sodium bis (2-ethylhexyl)-sulphosuccinate), water, gelatin and an organic solvent is presented for heptane. The stability of this organo- gel, when an enzyme is immobilized is discussed in terms of its reutilization in various esters synthesis.

The wide synthetic versatility of five membered rings containing phosphorus

The chemistry of cyclopentadiene rings has been widely studied. This review article deals with a similar chemistry of new compounds containing from 1 to 5 phosphorus atoms on the ring substituting the carbon atoms. The neutral rings containing one, two and three phosphorus atoms can be used as building blocks for the synthesis of new organic compounds containing phosphorus. These rings plus the anionic ones also show great potential as ligands in coordination chemistry. The aim of this article is to show how important this new area is and how diverse the chemistry related to a single type of ring can be.

Caracterização de catalisadores Cu/CeO2/Al2O3 por redução a temperatura programada e atividade para oxidação de CO

The kinetic parameters for the CO oxidation reaction using copper/alumina-modified ceria as catalysts were determined. The catalysts with different concentrations of the metals were prepared using impregnation methods. In addition, the reduction-oxidation behaviour of the catalysts were investigated by temperature-programmed reduction. The activity results show that the mechanism for CO oxidation is bifunctional : oxygen is activated on the anionic vacancies of ceria surface, while carbon monoxide is adsorbed preferentially on the higher oxidation copper site. Therefore, the reaction occurs on the interfacial active centers. Temperatures-programmed Reduction patterns show a higher disperdion when cerium oxide is present.

Filmes poliméricos ultrafinos produzidos pela técnica de automontagem: preparação, propriedades e aplicações

The self-assembly technique is a powerful tool to fabricate ultrathin films from organic compounds aiming at technological applications in molecular electronics. This relatively new approach allows molecularly flat films to be obtained on a simple and cheap fashion from various types of material, including polyelectrolytes, conducting polymers, dyes and proteins. The resulting multilayer films may be fabricated according to specific requirements since their structural and physical properties may be controlled at the molecular level. In this review we shall comment upon the evolution of preparation methods for ultrathin films, the process of adsorption and their main properties, as well as some examples of technological applications of layer-by-layer or self-assembled films.

Production of fungal protein by solid substrate fermentation of cactus Cereus peruvianus and Opuntia ficus indica

Agricultural wastes from cactus Cereus peruvianus and Opuntia ficus indica were investigated for protein production by solid substrate fermentation. Firstly, the polyelectrolytes were extracted and used in water cleaning as auxiliary of flocculation and coagulation. The remaining fibrous material and peels were used as substrate for fermentation with Aspergillus niger. Glucoamylase and cellulase were the main enzymes produced. Amino acids were determined by HPLC and protein by Lowry's method. After 120 hours of fermentation the protein increased by 12.8%. Aspartic acid (1.27%), threonine (0.97%), glutamic acid (0.88%), valine (0.70%), serine (0.68%), arginine (0.82%), and phenylalanine (0.51%) were the principal amino acids produced.

Estudo semi-empírico de ácidos hidroxâmicos: ácido formoidroxâmico e derivados do aleloquímico dimboa

Open chain hydroxamic acid (Hx) can exist as Z and E diastereomers of two tautomers, hydroxamic acid and hydroximic acid. The conformational stability of the formohydroxamic acid isomers evaluated by PM3 compared better to ab initio results from the literature than AM1 results. Structural data of the cyclic Hx 2,4-dihydroxy-7-metoxy-2H-1,4-benzoxazin-3(4 H)-one (DIMBOA) obtained by both semiempirical methods compared well to ab initio results. pKa data from the literature for derivatives of the aldolic isomer of DIMBOA were compared to the stability of the anions resulting from the loss of protons of their phenol and hydroxamic acid groups, determined as the difference in heat of formation between anionic and neutral forms, calculated by AM1 and PM3 methods. Good correlations between theoretical and experimental data were obtained for both semiempirical methods.

Deposição eletrolítica catódica e anódica simultâneas para minimizar interferências de cobre e chumbo na determinação espectrofotométrica de cádmio em água e alimentos via reação com Verde de Malaquita e iodeto

Simultaneous electrolytic deposition is proposed for minimization of Cu2+ and Pb2+ interferences on automated determination of Cd2+ by the Malachite Green-iodide reaction. During electrolysis of sample in a cell with two Pt electrodes and a medium adjusted to 5% (v/v) HNO3 + 0.1% (v/v) H2SO4 + 0.5 mol L-1 NaCl, Cu2+ is deposited as Cu on the cathode, Pb2+ is deposited as PbO2 on the anode while Cd2+ is kept in solution. With 60 s electrolysis time and 0.25 A current, Pb2+ and Cu2+ levels up to 50 and 250 mg L-1 respectively, can be tolerated without interference. With on-line extraction of Cd2+ in anionic resin minicolumn, calibration graph in the 5.00 - 50.0 µg Cd L-1 range is obtained, corresponding to twenty measurements per hour, 0.7 mg Malachite Green and 500 mg KI and 5 mL sample consumed per determination. Results of the determination of Cd in certified reference materials, vegetables and tap water were in agreement with certified values and with those obtained by GFAAS at 95% confidence level. The detection limit is 0.23 µg Cd L-1 and the RSD for typical samples containing 13.0 µg Cd L-1 was 3.85 % (n= 12).

Redução de poluentes de efluentes das indústrias de papel e celulose pela floculação/coagulação e degradação fotoquímica

The abatement of recalcitrant lignin macromolecules from effluents of pulp and paper industry was investigated by combined process. Flocculation and coagulation with aluminum sulfate and natural polyelectrolytes extracted from cactus Cereus peruvianus were used in the first step. After separation of solid residues by filtration, the photochemical methods using TiO2 as catalyst were employed for photocatalytic degradation of lignin compounds from solution. The abatement of lignin compounds after flocculation and coagulation was 46%, and after the overall process, the pollutants reduction observed were 66%. The remaining organic compounds may be removed by any biological treatment.

Cromatografia de troca-iônica aplicada ao isolamento da fração ácida do óleo de copaíba (Copaifera multijuga) e da sacaca (Croton cajucara)

Plant extracts are usually complex mixtures which contain several molecules of different sizes with varied functional groups. Such extracts are a challenge to the chemist of natural products. Ion exchange chromatography in non-aqueous medium, used for separation of basic or acidic fractions from plant extracts, is an important unit operation in preparative scale separations. Anionic macroporous resin in non-aqueous medium was used with success in this study for separation of the acid fraction of Copaifera multijuga (Copaiba oil), rich in labdanic diterpenes and for the methanolic extract of Croton cajucara (acetyl aleuritoric acid).

Ecomateriais: desenvolvimento e aplicação de materiais porosos funcionais para proteção ambiental

Fundamental aspects of the conception and applications of ecomaterials, in particular porous materials in the perspective of green chemistry are discussed in this paper. General recommendations for description and classification of porous materials are reviewed briefly. By way of illustration, some case studies of materials design and applications in pollution detection and remediation are described. It is shown here how different materials developed by our groups, such as porous glasses, ecomaterials from biomass and anionic clays were programmed to perform specific functions. A discussion of the present and future of ecomaterials in green chemistry is presented along with important key goals.

Recuperação de cádmio de baterias níquel-cádmio via extração seletiva com tributilfosfato (TBP)

This work describes a recovery process of cadmium from spent nickel-cadmium batteries by a new hydrometallurgical route based on the selective extraction in hydrochloric acid medium with tributylphosphate (TBP), alone or dissolved in kerosene. The best results were obtained when TBP concentration was at least 75 vol%. Nickel extraction was negligible under these conditions. It was isolated after processing the rafinate through an anionic ion-exchange column. Final wastes generated are basically sodium chloride solutions, with no turbidity, color or heavy metals present in significant amounts.

Electrical and magnetic properties of new compounds of the conductor anion [Ni(dmit)2]- and nitronyl nitroxide magnetic radicals

Three compounds have been synthesized with formulae [3-MeRad][Ni(dmit)2] (1), [4-MeRad][Ni(dmit)2] (2) and [4-PrRad][Ni(dmit)2] (3) where [Ni(dmit)2]- is an anionic pi-radical (dmit = 1,3-dithiol-2-thione-4,5-dithiolate) and [3-MeRad]+ is 3-N-methylpyridinium alpha-nitronyl nitroxide, [4-MeRad]+ is 4-N-methylpyridinium alpha-nitronyl nitroxide and [4-PrRad]+ is 4-N-propylpyridinium alpha-nitronyl nitroxide. The temperature-dependent magnetic susceptibility of 1 revealed that an antiferromagnetic interaction operates between the 3-MeRad+ radical cations with exchange coupling constants of J1 = - 1.72 cm-1 and antiferromagnetism assigned to the spin ladder chains of the Ni(dmit)2 radical anions. Compound 1 exhibits semiconducting behavior and 3 presents capacitor behavior in the temperature range studied (4 - 300 K).