A new route to furanoeremophilane sesquiterpenoids. Synthesis of Senecio metabolites (+/-)-6-hydroxyeuryopsin, (+/-)-1,10-epoxy-6-hydroxyeuryopsin, (+/-)-toluccanolide A and (+/-)-toluccanolide C

A new strategy for the synthesis of sesquiterpenoids of the furanoeremophilane family was developed in which the tricyclic nucleus was assembled in an A + C -> A - C -> A - B - C sequence. The A - C connection was made via coupling of a cyclohexenylmethyl bromide with a stannylfuran under "ligandless" Stille conditions, and the key cyclization which closed ring B was accomplished with complete stereocontrol by intramolecular formylation of a 2-silylfuran in the presence of trimethylsilyl triflate. This route was used to complete the first total syntheses of the furanoeremophilane 6-hydroxyeuryopsin and the eremophilenolides toluccanolide A and toluccanolide C, as well as a formal synthesis of 1,10-epoxy-6-hydroxyeuryopsin.

Synthesis of FimH receptor-active manno-oligosaccharides by reverse hydrolysis using alpha-mannosidases from Penicillium citrinum, Aspergillus phoenicis and almond

Recombinant Penicillium citrinum alpha-1,2-mannosidase, expressed in Aspergillus oryzae, was employed to carry out regioselective synthesis of alpha-D-mannopyranosyl-(1-->2)-D-mannose. Yields (w/w) of 16.68% disaccharide, 3.07% trisaccharide and 0.48% tetrasaccharide were obtained, with alpha1-->2 linkages present at 98.5% of the total linkages formed. Non-specific alpha-mannosidase from almond was highly efficient in reverse hydrolysis and oligosaccharide yields of 45-50% were achieved. The products of the almond mannosidase were a mixture of disaccharides (30.75%, w/w), trisaccharides (12.26%, w/w) and tetrasaccharides (1.89%, w/w) with 1-->2, 1-->3 and 1-->6 isomers. alpha-1,2-linkage specific mannosidase from P. citrinum and alpha-1,6-linkage-specific mannosidase from Aspergillus phoenicis were used in combination to hydrolyse the respective linkages from the mixture of isomers, resulting in alpha-D-mannopyranosyl-(1-->3)-D-mannose in 86.4% purity. The synthesised oligosaccharides can potentially inhibit the adhesion of pathogens by acting as 'decoys' of receptors of type-1 fimbriae carried by enterobacteria.

Regioselective synthesis of mannobiose and mannotriose by reverse hydrolysis using a novel 1,6-alpha-D-mannosidase from Aspergillus phoenicis

A novel 1,6-alpha-D-mannosidase was produced by Aspergillus phoenicis grown on a commercial manno-oligosaccharide preparation in liquid culture. The enzyme hydrolysed only alpha-D-Manp-(1 --> 6)-D-Manp and did not act on alpha-D-Manp-(1 --> 2)-D-Manp, or alpha-D-Manp-(1 --> 3)-D-Manp. The 1,6-alpha-D-mannosidase was used for synthesis of manno-oligosaccharides by reverse hydrolysis reaction. The highest yields, expressed as percentages (w/w) of total sugar, were similar to21% mannobiose and similar to5% mannotriose, and they were obtained with 45% (w/w) initial mannose concentration at pH 4.5 after 12 days incubation at 55 degreesC. The disaccharide and trisaccharide products were separated and their structures determined by methylation analysis. Only 1-6 linkages were found in both of them. (C) 2003 Elsevier B.V. All rights reserved.

BbgIV is an important Bifidobacterium β-galactosidase for the synthesis of prebiotic galactooligosaccharides at high temperatures

The individual contribution of four β-galactosidases present in Bifidobacterium bifidum NCIMB 41171 towards galactooligosaccharides (GOS) synthesis was investigated. Although the β-galactosidase activity of the whole cells significantly decreased as a function of temperature (40 to 75 °C), GOS yield was at its maximum at 65 °C. Native-PAGE electrophoresis of the whole cells showed that the contribution of BbgIII and BbgIV towards GOS synthesis increased as the temperature increased. Moreover, BbgIII and BbgIV were found to be more temperature stable and to produce a higher GOS yield than BbgI and BbgII, when used in their free form. The GOS yield using BbgIV was 54.8 % (% of total carbohydrates) and 63.9 % (% lactose converted to GOS) at 65 °C from 43 % w/w lactose. It was shown that BbgIV is the most important β-galactosidase in B. bifidum NCIMB 41171 and can be used for GOS synthesis at elevated temperatures.

Malonato complexes of oxidovanadium(IV): synthesis, structural characterization and exploration of their insulin mimetic properties

Several bis-malonatooxidovanadium(IV) complexes of the general type [M(2)(H2(O))(n)][VO(mal)(2)(H(2)O)] (where M = Li(1), Na(2), K(3), Cs(4) and NH4(5); n = 3.5, 1, 3, 1 and 1, respectively) were isolated in good yield and high purity. These complexes were fully characterized by various physicochemical techniques (elemental analysis, UV- Vis, IR, EPR, CV, etc.) complexes 1, 2 and 3 were structurally characterized by single crystal X- ray diffraction technique. In vivo antidiabetic properties of bis- malonato complexes 1, 2, 3 and 5 have been studied using Streptozotocin induced diabetic rats. Significant lowering of blood sugar level has been noticed. At the same time these complexes were found to regulate secondary pathophysiological complications like liver damage and lowering of the total antioxidant status (TAS) in diabetic rats. Results of these study are expected to a expand the possibility of designing new oxidovanadium(IV) complexes of O, O chelating ligands with significant antidiabetic properties

High yield production of a soluble bifidobacterial β-galactosidase (BbgIV) inE. coliDH5α with improved catalytic efficiency for the synthesis of prebiotic galactooligosaccharides

The bifidobacterial β-galactosidase (BbgIV) was produced in E. coli DH5α at 37 and 30 °C in a 5 L bioreactor under varied conditions of dissolved oxygen (dO2) and pH. The yield of soluble BbgIV was significantly (P < 0.05) increased once the dO2 dropped to 0–2% and remained at such low values during the exponential phase. Limited dO2 significantly (P < 0.05) increased the plasmid copy number and decreased the cells growth rate. Consequently, the BbgIV yield increased to its maximum (71–75 mg per g dry cell weight), which represented 20–25% of the total soluble proteins in the cells. In addition, the specific activity and catalytic efficiency of BbgIV were significantly (P < 0.05) enhanced under limited dO2 conditions. This was concomitant with a change in the enzyme secondary structure, suggesting a link between the enzyme structure and function. The knowledge generated from this work is very important for producing BbgIV as a biocatalyst for the development of a cost-effective process for the synthesis of prebiotic galactooligosaccharides from lactose.

Freshwater and heat transports from global ocean synthesis

[1] An eddy-permitting ¼° global ocean reanalysis based on the Operational Met Office FOAM data assimilation system has been run for 1989–2010 forced by ERA-Interim meteorology. Freshwater and heat transports are compared with published estimates globally and in each basin, with special focus on the Atlantic. The meridional transports agree with observations within errors at most locations, but where eddies are active the transports by the mean flow are nearly always in better agreement than the total transports. Eddy transports are down gradient and are enhanced relative to a free run. They may oppose or reinforce mean transports and provide 40–50% of the total transport near midlatitude fronts, where eddies with time scales <1 month provide up to 15%. Basin-scale freshwater convergences are calculated with the Arctic/Atlantic, Indian, and Pacific oceans north of 32°S, all implying net evaporation of 0.33 ± 0.04 Sv, 0.65 ± 0.07 Sv, and 0.09 ± 0.04 Sv, respectively, within the uncertainty of observations in the Atlantic and Pacific. The Indian is more evaporative and the Southern Ocean has more precipitation (1.07 Sv). Air-sea fluxes are modified by assimilation influencing turbulent heat fluxes and evaporation. Generally, surface and assimilation fluxes together match the meridional transports, indicating that the reanalysis is close to a steady state. Atlantic overturning and gyre transports are assessed with overturning freshwater transports southward at all latitudes. At 26°N eddy transports are negligible, overturning transport is 0.67 ± 0.19 Sv southward and gyre transport is 0.44 ± 0.17 Sv northward, with divergence between 26°N and the Bering Strait of 0.13 ± 0.23 Sv over 2004–2010.

Vertical structure and physical processes of the Madden-Julian oscillation: synthesis and summary

The "Vertical structure and physical processes of the Madden-Julian oscillation (MJO)" project comprises three experiments, designed to evaluate comprehensively the heating, moistening and momentum associated with tropical convection in general circulation models (GCMs). We consider here only those GCMs that performed all experiments. Some models display relatively higher or lower MJO fidelity in both initialized hindcasts and climate simulations, while others show considerable variations in fidelity between experiments. Fidelity in hindcasts and climate simulations are not meaningfully correlated. The analysis of each experiment led to the development of process-oriented diagnostics, some of which distinguished between GCMs with higher or lower fidelity in that experiment. We select the most discriminating diagnostics and apply them to data from all experiments, where possible, to determine if correlations with MJO fidelity hold across scales and GCM states. While normalized gross moist stability had a small but statistically significant correlation with MJO fidelity in climate simulations, we find no link with fidelity in medium-range hindcasts. Similarly, there is no association between timestep-to-timestep rainfall variability, identified from short hindcasts, and fidelity in medium-range hindcasts or climate simulations. Two metrics that relate precipitation to free-tropospheric moisture--the relative humidity for extreme daily precipitation, and variations in the height and amplitude of moistening with rain rate--successfully distinguish between higher- and lower-fidelity GCMs in hindcasts and climate simulations. To improve the MJO, developers should focus on relationships between convection and both total moisture and its rate of change. We conclude by offering recommendations for further experiments.

Synthesis and characterization of glass-ceramic microspheres for thermotherapy

Glass microspheres containing radionuclides are used to treat liver cancer. A promising alternative therapy is being developed based on the magnetic hyperthermia which is related to the heat supplied by a magnetic material under an alternating current magnetic field. The advantage of this option is that most of killed cells are cancer cells which are more susceptible to the temperature raise. In the present work aluminum iron silicate glasses containing minor glass modifiers and nucleating agents were synthesized as irregular shape particles which were further transformed in microspheres by using a petrol liquefied gas-oxygen torch. The optimized processing parameters which lead to microspheres that give a response to the magnetic field were determined. The dissolution rate in water at 90 degrees C was determined to be 3 x 10(-8) g cm(-2) min(-1). The microsphere size distribution was determined by laser scattering. The crystalline phase responsible for the ferromagnetic response was identified as magnetite. Since this phase has a high saturation magnetization and high Curie temperature, it is potentially useful for biomedical applications. The hysteresis magnetic loop was measured for materials produced in different conditions, and some of them showed to be appropriated for thermotherapy. The ratio Fe(3+)/Fe(total) was determined by Mossbauer spectroscopy. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis, characterization and adsorption properties of porous mixed valent diruthenium(II,III)-terephthalate and diruthenium(II,III)-adipate polymers

Two porous mixed valent diruthenium(II,III)-dicarboxylate compounds have been prepared and characterized by spectroscopic methods, X-ray diffraction and thermogravimetry. Crystalline solids of [Ru(2)(tere)(2)Cl] center dot 3.5H(2)O (tere=terephthalate) and [Ru(2)(adip)(2)Cl] center dot 1.5H(2)O (adip=adipate) consist of extended chains in which polymeric layers of multiply metal-metal bonded [Ru(2)](5+) cores are bridged by dicarboxylate ligands in paddlewheel type geometries. Units of [Ru(2)(dicarboxylate)(2)](n)(+) are linked by axial bridging chloride ions generating three-dimensional networks. The polymers loose non-bonded water molecules at low temperatures but do not undergo thermal decomposition below 280-300 degrees C. Both of compounds exhibit high BET surface areas, [Ru(2)(tere)(2)Cl]: 235 m(2) g(-1) and [Ru(2)(adip)(2)Cl]: 281 m(2) g(-1), and occlude similar numbers of mol of N(2) per mol of metal. The terephthalate ligand generated an organized structure with supermicropores (total pore size of 0.24 cm(3) g(-1)) while the adipate ligand led to a mesoporous structure (total pore sizes of 0.47 cm(3) g(-1)) for the corresponding diruthenium(II,III)-dicarboxylate polymers. (c) 2008 Elsevier B.V. All rights reserved.

IgA sérica, secretora, IgE total e estado nutricional em crianças com infecções por enteroparasitas

Infections for intestinal parasites are one of the main morbidade causes in humans and, its relationships with socioeconomic levels and hygiene conditions in countries in development are already very established. Many works, even so, they are being accomplished to elucidate the complex interactions among nutrition, these infections and answer imunológica, because it is seen that malnutrition commits the immunity increasing the susceptibilidade for infectious diseases and these for its time can harm the state human nutricional. It is known that sponge helmínticos they stimulate synthesis of IgE so much policlonal as specific for the same ones and that IgA secretora, main imunoglobulina of defense of the mucous ones, can act against protozoa as the Giardia lamblia and against helmintos as Trichuris tichiura and Strongyloides stercorales. Some studies show that the malnutrition energy protéica influences in the production of these answers, but some authors show results divergentes. In this work it was evaluated the levels of total IgE, IgA sérica and secretora, contagem of sanguine eosinófilos, levels of proteins séricas and state nutricional, in 103 children of low socioeconomic level, to discover a correlation between those and infection for enteroparasitas. They participated in the study children of both sexes, with age of 3 to 6 years, visitors of the same creche and residents in a neighborhood with precarious hygiene conditions and basic saneamento, in the city of Christmas. The obtained results showed that the faulty environmental and socioeconomic conditions favored to a high infection frequency for enteroparasitas, mainly Trichuris trichiura and Ascaris lumbricoides between the helmintos and Endolimax sleep and Giárdia lamblia among the protozoa. Light malnutrition without deficit protéico was observed in 30% of the children, which didn't also present significant deficiencies of IgA sérica and secretora. The sponged children

Síntese de catalisadores nanoporosos na ausência total e parcial de direcionadores orgânicos para pirólise catalítica de óleos pesados e intermediários

The processing of heavy oil produced in Brazil is an emergency action and a strategic plan to obtain self-sufficiency and economic surpluses. Seen in these terms, it is indispensable to invest in research to obtain new catalysts for obtaining light fraction of hydrocarbons from heavy fractions of petroleum. This dissertation for the degree of Doctor of Philosophy reports the materials preparation that combine the high catalytic activity of zeolites with the greater accessibility of the mesoporosity, more particularly the HZSM-5/MCM-41 hybrid, done by synthesis processes with less environmental impact than conventional ones. Innovative methodologies were developed for the synthesis of micro-mesoporous hybrid material by dual templating mechanism and from crystalline zeolitic aluminosilicate in the absence of organic template. The synthesis of hybrid with pore bimodal distribution took place from one-single organic directing agent aimed to eliminate the use of organic templates, acids of any kind or organic solvents like templating agent of crystalline zeolitic aluminosilicate together with temperature-programmed microwave-assisted, making the experimental procedures of preparation most practical and easy, with good reproducibility and low cost. The study about crystalline zeolitic aluminosilicate in the absence of organic template, especially MFI type, is based on use of H2O and Na+ cation playing a structural directing role in place of an organic template. Advanced characterization techniques such as X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Highresolution Transmission Electron Microscopy (HRTEM), Adsorption of N2 and CO2, kinetic studies by Thermogravimetric Analysis (TGA) and Pyrolysis coupled to Gas Chromatography/Mass Spectrometry (Pyrolysis-GC/MS) were employed in order to evaluate the synthesized materials. Achieve the proposed objectives, has made available a set of new methodologies for the synthesis of zeolite and hybrid micro-mesoporous material, these suitable for catalytic pyrolysis of heavy oils aimed at producing light fraction

Replacement of dicalcium phosphate by rock phosphate in cattle diets: nutrients digestibility, plasma parameters, ruminal fermentation and microbial synthesis efficiency

Este estudo foi conduzido para avaliar os efeitos da substituição do fosfato bicálcico pelo fosfato de rocha na dieta de bovinos em crescimento. Foram determinados a digestibilidade aparente das dietas, a absorção aparente do fósforo, cálcio e flúor, o pH ruminal, a concentração de amônia ruminal, a eficiência microbiana e o fósforo no plasma utilizando-se cinco bovinos da raça Holandesa Preto-e-Branco, fistulados, pesando entre 275 e 283 kg. O delineamento estatístico foi um quadrado latino 5 × 5 e as dietas consistiram de 0, 25, 50, 75 e 100% de substituição do fosfato bicálcico pelo fosfato de rocha no suplemento mineral. A adição de fosfato de rocha nas dietas ocasionou aumento linear na ingestão, no fluxo omasal, no fluxo fecal e no desaparecimento total do flúor. As dietas não diferiram quanto à absorção aparente do cálcio, assim como em relação à ingestão, excreção, digestão e digestibilidades aparentes parcial e total da matéria seca, matéria orgânica, proteína bruta, fibra em detergente neutro e carboidratos não-fibrosos. O fósforo no plasma não foi influenciado pelos tratamentos e a média foi de 5,93 mg/dL. Não houve diferença para o pH ruminal e concentração de amônia ruminal. A substituição do fosfato bicálcico não afetou a síntese microbiana aparente e verdadeira de proteína. A total substituição do fosfato bicálcico pelo fosfato de rocha em suplementos minerais em bovinos em crescimento não afetou o ambiente ruminal e a síntese de proteína no rúmen. Assim, a substituição do fosfato bicálcico em dietas para bovinos em crescimento diminui a absorção de fósforo e deveria ser vista com cuidado dependendo dos requerimentos.

Digestibilidade total e parcial e balanço nitrogenado em bovinos em pastejo no período das águas recebendo suplementos com nitrogênio não-proteico e/ou proteína verdadeira

Objetivou-se avaliar o efeito de diferentes relações entre proteína verdadeira e nitrogênio não-proteico sobre a digestibilidade, a síntese de proteína microbiana e o balanço de compostos nitrogenados em bovinos em pastejo durante o período das águas. Foram utilizados cinco novilhos mestiços Holandês × Zebu, castrados, com peso vivo inicial de 335±35 kg fistulados no rúmen e no abomaso. Os tratamentos foram: controle (somente pasto); e suplementos com ureia; com 2/3 de compostos nitrogenados oriundos da ureia e 1/3 de compostos nitrogenados oriundos da albumina; com 1/3 de compostos nitrogenados oriundos da ureia e 2/3 de compostos nitrogenados oriundos da albumina; e com albumina. Foram fornecidos 200 g/dia de proteína bruta (PB) a partir dos suplementos. O experimento foi conduzido segundo delineamento em quadrado latino 5 × 5, com cinco períodos experimentais, cada um de 15 dias. A suplementação não afetou os coeficientes de digestibilidade total nem o teor de nutrientes digestíveis totais da dieta; elevou as estimativas do coeficiente de digestibilidade aparente ruminal da PB, que migraram de negativa, no tratamento controle, para positivas, porém não diferentes de zero, nos tratamentos envolvendo suplementação. O fornecimento de suplementos elevou a concentração de nitrogênio amoniacal ruminal. O balanço de compostos nitrogenados aumentou com a suplementação. A substituição de ureia por albumina influenciou de forma cúbica o balanço de compostos nitrogenados, cuja estimativa foi maior para o suplemento com 1/3 de PB oriunda da ureia. A eficiência de síntese microbiana no rúmen não foi influenciada pelo fornecimento ou pela composição dos suplementos. A suplementação de bovinos em pastejo com fontes de compostos nitrogenados degradáveis durante o período das águas amplia a eficiência de uso do pasto, principalmente por ampliar a retenção de compostos nitrogenados no organismo.