Chemoselective cross-coupling Suzuki-Miyaura reaction of (Z)-(2-chlorovinyl)tellurides and potassium aryltrifluoroborate salts

An ultrasound-assisted synthesis of functionalized vinylic chlorides is described by palladium-catalyzed cross-coupling reaction of potassium aryltrifluoroborate salts and (Z)-2-chloro vinylic tellurides. This procedure offers easy access to vinylic chlorides architecture that contains sterically demanding groups in good yields. (C) 2008 Elsevier Ltd. All rights reserved.

Physicochemical characterization of two deproteinized bovine xenografts

Calcium phosphate salts, or more specifically hydroxyapatite, are products of great interest in the fields of medical and dental science due to their biocompatibility and osteoconduction property. Deproteinized xenografts are primarily constituted of natural apatites, sintered or not. Variations in the industrial process may affect physicochemical properties and, therefore, the biological outcome. The purpose of this work was to characterize the physical and chemical properties of deproteinized xenogenic biomaterials, Bio-Oss (Geistlich Biomaterials, Wolhuser, Switzerland) and Gen-Ox (Baumer S.A., Brazil), widely used as bone grafts. Scanning electron microscopy, infrared region spectroscopy, X-ray diffraction, thermogravimetry and degradation analysis were conducted. The results show that both materials presented porous granules, composed of crystalline hydroxyapatite without apparent presence of other phases. Bio-Oss presented greater dissolution in Tris-HCl than Gen-Ox in the degradation test, possibly due to the low crystallinity and the presence of organic residues. In conclusion, both commercial materials are hydroxyapatite compounds, Bio-Oss being less crystalline than Gen-Ox and, therefore, more prone to degradation.

Níveis de concentrado e sais de cálcio de ácidos graxos para novilhos terminados em confinamento

Objetivou-se avaliar o efeito do nível de concentrado e dos sais de cálcio de ácidos graxos (SCAG) sobre o desempenho e qualidade da carne de novilhos terminados em confinamento. Sessenta novilhos Nelore e cruza Nelore foram divididos em quatro grupos e confinados por um período de 85 dias com as seguintes dietas: (BC) 46,7% de concentrado; (BC-SCAG) dieta BC acrescida de 3% de SCAG; (AC) dieta contendo 76,6% de concentrado e (AC-SCAG) dieta AC com 3% de SCAG. O nível de concentrado não influenciou o ganho médio diário, a espessura de gordura subcutânea e a área de olho de lombo, mas as dietas AC aumentaram o peso (P=0,0011) e o rendimento (P<0,0001) de carcaça, além da força de cisalhamento (P=0,0438). Animais alimentados com as dietas AC apresentaram maior peso (P=0,0011) e rendimento (P<0,0001) de carcaça em relação aos animais do tratamento BC. Os SCAG aumentaram o ganho de peso em dietas de AC (P=0,0311), mas sem efeito nas dietas BC. Animais tratados com as dietas contendo SCAG apresentaram maior peso (P=0,0133) e rendimento de carcaça (P=0,0160), mas sem diferenças na espessura de gordura subcutânea, área de olho de lombo e força de cisalhamento. Dietas de alto concentrado e os SCAG melhoraram as características quantitativas (peso e rendimento) das carcaças de bovinos na fase de terminação e podem ser utilizadas pelos produtores como alternativa para melhorar a eficiência do sistema de produção.

Consumo, desempenho e parâmetros econômicos de novilhos Nelore e F1 Brangus x Nelore terminados em pastagens, suplementados com mistura mineral e sal nitrogenado com uréia ou amiréia

Avaliou-se o efeito da suplementação protéica (40% PB) com amiréia ou uréia sobre o consumo de suplemento, desempenho e características econômicas de novilhos terminados em pastagens. Foram utilizados 120 novilhos com 19 meses de idade e 358kg, sendo 60 Nelore e 60 F1 Brangus x Nelore, divididos em três tratamentos com 20 animais, alojados em piquetes de Brachiaria brizantha cv. Marandu de 10 hectares cada, totalizando 120 hectares, sendo dois piquetes por grupo genético e tratamento, pastejados alternadamente a cada pesagem (42 dias). Os tratamentos consistiram em mistura mineral com amiréia-150S (AM), mistura mineral com uréia+milho+enxofre (UR) e mistura mineral (MM). As médias de consumo de suplemento dos animais F1 foram de 206,1; 145,9 e 73,1g/dia, e as dos animais Nelore, 236,0; 205,1 e 94,3g/dia para os tratamentos AM, UR e MM, respectivamente. Para os novilhos Nelore, houve efeito (P<0,05) do suplemento sobre o peso de abate (PA), sendo a média do tratamento UR, 518,85kg, mais alta que a dos demais, 491,89 e 485,20kg, respectivamente, para AM e MM. Para os novilhos F1, foi significativo o efeito da suplementação protéica (P<0,05), com médias de 515,90 e 520,15kg, respectivamente, para os tratamentos UR e AM. A suplementação protéica proporcionou bom desempenho em animais F1 durante períodos de abundância de forragem. O uso de uréia apresentou melhor viabilidade econômica.

Síntese, caracterização e análise térmica dos sais de lítio, sódio e potássio do ácido palmítico e do seu éster etílico

Alkaline salts of the palmitic acid were synthesized and characterized from aqueous and ethanolic medium. The salts were characterized by elemental analysis (EA) and infrared spectroscopy (IR). EA and IR, being its synthesis comproved, also characterized the ethyl palmitate. All the salts and the ester were submitted to thermal analysis using thermogravimetry (TG), and differential thermal analysis (DTA) in the temperature ranging from room to 700 ºC under air dynamic atmosphere. Differential scanning calorimetry (DSC) measurements were taken from -90 ºC up to temperatures close to the starting of the decomposition temperature, determined by thermogravimetry, using heating and cooling cycles.

Estudos termoanalíticos de sais de sódio e potássio de ditiocarbamatos em atmosfera oxidante

Thermoanalytical behavior of sodium and potassium salts of pyrrolidinedithiocarbamate (pyr), piperidineditiocarbamate (pip), morpholinedithiocarbamate (mor), hexametileneiminedithiocarbamate (hex), were investigated. In a first step the salts were synthesized and characterized by infrared spectroscopy (FTIR), ¹H and 13C nuclear magnetic resonance (NMR) and elementar analysis. Finally, thermal analytical (TG/DTG and DSC) studies were performed in order to evaluate the thermal stability, as well as the pathways of the thermal decomposition based in the intermediate and final decomposition products.

Reações de oxidação de derivados de cis-octalinas promovidas por trinitrato de tálio (TTN)

The reaction of ten cis-octalins and cis-octalones with thallium trinitrate (TTN) leads to different products, depending mainly on the substitution pattern of the substrate. Functionalized cis-hydrindanes were obtained from the reaction of 1,2,3,4,4a,5,8,8a-octahydro-4a-methylnaphthalene and of 1,2,3,4,4a,5,8,8a-octahydro-4a,7-dimethylnaphthalene with TTN in acetonitrile, whereas a cyclic ether was formed treating 1,2,3,4,4a,5,8,8a-octahydro-6,8a-dimethylnaphthalen-1-ol with TTN in trimethylorthoformate (TMOF).

Cálcio dietético: estratégias para otimizar o consumo

O cálcio é um nutriente essencial necessário em diversas funções biológicas. Estudos têm demonstrado a associação entre o baixo consumo de cálcio e doenças crônicas, entre elas osteoporose, câncer de colón, hipertensão arterial e obesidade. Entretanto, grande parte da população brasileira apresenta consumo de cálcio abaixo do recomendado. Este artigo objetiva revisar os fatores endógenos (idade e estado hormonal) e exógenos (fitatos, oxalatos, sódio, compostos bioativos e vitamina D) que influenciam a absorção do cálcio, bem como as principais metodologias utilizadas para avaliar a absorção e biodisponibilidade desse nutriente. Discorre-se sobre os possíveis fatores para o baixo consumo de cálcio: 1) Hábito alimentar - substituição de leite por bebidas com baixo teor de cálcio como o refrigerante, refeições realizadas fora de casa e a não realização de refeições como o café da manhã; 2) Alto custo dos alimentos fontes de cálcio. Além disso, este artigo discute as estratégias para otimizar o consumo do cálcio, que incluem: 1) Aumentar o conhecimento sobre a importância do consumo de cálcio para a saúde e as principais fontes alimentares desse nutriente; 2) Aumentar a disponibilidade de alimentos fortificados com cálcio; 3) Uso de suplementos em grupos específicos - quando e como administrar os sais de cálcio.

Productive performance and composition of milk protein fraction in dairy cows supplemented with fat sources

The objective of this study was to evaluate the use of fat sources in rations for lactating cows on the productive performance and composition of milk protein fraction. Twelve Holstein cows were used, grouped in three balanced 4 × 4 Latin squares, fed with the following rations: control; refined soybean oil; whole raw soybean; and calcium salts of unsaturated fatty acid (Megalac-E). Dry matter and nutrient intake, and daily milk production were evaluated. The samples used to analyze milk composition were collected in two alternate days and were obtained from two daily milking. Milk composition and total nitrogen, non-protein nitrogen and non-casein nitrogen ratios were analyzed. The casein, serum protein and true protein ratios were obtained by difference. Dry matter and nutrient intakes were lower when cows received the diet containing calcium salts of fatty acids, in relation to the control diet. Among the diets with fat sources, the one with whole raw soybean and calcium salts decreased milk production. There was no effect of fat sources added to the diet on crude protein, non-protein nitrogen, non-casein nitrogen, true protein, casein, casein/milk true protein ratio and serum protein. Similarly, the experimental diets did not influence the protein fractions when expressed in percentage of milk crude protein. The utilization of fat sources in diets changes milk production and composition of lactating cows, but does not influence the composition of milk protein fractions.

Parâmetros sanguíneos de vacas leiteiras suplementadas com diferentes fontes de gordura

O objetivo deste trabalho foi avaliar a utilização de diferentes fontes de gordura nas rações de vacas em lactação e seus efeitos sobre o consumo de matéria seca e as concentrações dos parâmetros sangüíneos. Foram utilizadas 12 vacas da raça Holandês, agrupadas em três quadrados latinos balanceados 4x4 e alimentadas com as seguintes rações: 1) controle; 2) óleo de soja refinado; 3) grão de soja in natura; e 4) sais de cálcio de ácidos graxos (Megalac-E). As concentrações de colesterol total, colesterol, lipoproteína de baixa densidade (LDL) e colesterol de alta densidade (HDL) foram maiores (P<0,05) para as vacas alimentadas com as rações contendo fontes de gordura em relação à ração controle. As concentrações de uréia e nitrogênio ureico no soro foram semelhantes entre as rações utilizadas, com exceção da ração contendo sais de cálcio de ácidos graxos, que apresentou concentrações menores (P<0,05). O consumo de matéria seca foi menor (P<0,05) nas vacas que receberam sais de cálcio nas rações. Os animais que receberam a ração contendo grão de soja como fonte de gordura apresentaram menor (P<0,05) produção de leite quando comparada às demais rações utilizadas. A utilização de fontes de gordura em rações de vacas em lactação alterou os parâmetros sanguíneos, dependendo da fonte de gordura utilizada.

Modulation of extracellular matrix by nutritional hepatotrophic factors in thioacetamide-induced liver cirrhosis in the rat

Nutritional substances associated to some hormones enhance liver regeneration when injected intraperitoneally, being denominated hepatotrophic factors (HF). Here we verified if a solution of HF (glucose, vitamins, salts, amino acids, glucagon, insulin, and triiodothyronine) can revert liver cirrhosis and how some extracellular matrices are affected. Cirrhosis was induced for 14 weeks in 45 female Wistar rats (200 mg) by intraperitoneal injections of thioacetamide (200 mg/kg). Twenty-five rats received intraperitoneal HF twice a day for 10 days (40 mL·kg-1·day-1) and 20 rats received physiological saline. Fifteen rats were used as control. The HF applied to cirrhotic rats significantly: a) reduced the relative mRNA expression of the genes: Col-α1 (-53%), TIMP-1 (-31.7%), TGF-β1 (-57.7%), and MMP-2 (-41.6%), whereas Plau mRNA remained unchanged; b) reduced GGT (-43.1%), ALT (-17.6%), and AST (-12.2%) serum levels; c) increased liver weight (11.3%), and reduced liver collagen (-37.1%), regenerative nodules size (-22.1%), and fibrous septum thickness. Progranulin protein (immunohistochemistry) and mRNA (in situ hybridization) were found in fibrous septa and areas of bile duct proliferation in cirrhotic livers. Concluding, HF improved the histology and serum biochemistry of liver cirrhosis, with an important reduction of interstitial collagen and increased extracelullar matrix degradation by reducing profibrotic gene expression.

Modelo de suplementação nutricional com fatores hepatotróficos aumenta proliferação celular em fígado de ratos sadios

Foram avaliados dois protocolos de administração, em ratos sadios, de uma solução de fatores hepatotróficos (FH), composta por aminoácidos, vitaminas, sais minerais, glicose, insulina, glucagon e triiodotironina (T3). A solução foi administrada durante 10 dias, 40mg/kg/dia, i.p., em duas, grupo 2xFH (n=15), ou três doses, grupo 3xFH (n=15), diárias. Foram observados os efeitos na proliferação celular dos hepatócitos, na angiogênese e na matriz extracelular hepática, assim como as possíveis reações adversas. Os animais dos grupos 2xFH e 3xFH apresentaram aumento da massa hepática de 30,1% e 22,5%, respectivamente, em relação ao grupo-controle (CT; n=15). O índice de proliferação hepatocelular foi maior nos grupos 2xFH (1,4%) e 3xFH (1,2%) em relação ao grupo CT (0,53%), e a densitometria relativa do fator de crescimento do endotélio vascular pelo imunoblot não revelou diferença estatística entre os três grupos. Nos grupos 2xFH e 3xFH, houve redução do colágeno intersticial em relação ao grupo CT. A solução de FH estimulou o crescimento hepático e reduziu o volume de colágeno perissinusoidal. A administração em três doses diárias resultou em mortalidade de 26,7%, possivelmente pelo excessivo estresse da manipulação e pela menor adaptação fisiológica dos ratos, o que não ocorreu nos grupos 2xFH e CT. Para esse tipo de abordagem em ratos, o procedimento experimental mais apropriado, seguro, com melhor chance de adaptação dos animais e com resultados significativos é a aplicação dos FH em duas doses diárias.

A possible role of ground-based microorganisms on cloud formation in the atmosphere

The formation of clouds is an important process for the atmosphere, the hydrological cycle, and climate, but some aspects of it are not completely understood. In this work, we show that microorganisms might affect cloud formation without leaving the Earth's surface by releasing biological surfactants (or biosurfactants) in the environment, that make their way into atmospheric aerosols and could significantly enhance their activation into cloud droplets. In the first part of this work, the cloud-nucleating efficiency of standard biosurfactants was characterized and found to be better than that of any aerosol material studied so far, including inorganic salts. These results identify molecular structures that give organic compounds exceptional cloud-nucleating properties. In the second part, atmospheric aerosols were sampled at different locations: a temperate coastal site, a marine site, a temperate forest, and a tropical forest. Their surface tension was measured and found to be below 30 mN/m, the lowest reported for aerosols, to our knowledge. This very low surface tension was attributed to the presence of biosurfactants, the only natural substances able to reach to such low values. The presence of strong microbial surfactants in aerosols would be consistent with the organic fractions of exceptional cloud-nucleating efficiency recently found in aerosols, and with the correlations between algae bloom and cloud cover reported in the Southern Ocean. The results of this work also suggest that biosurfactants might be common in aerosols and thus of global relevance. If this is confirmed, a new role for microorganisms on the atmosphere and climate could be identified.

Cloud condensation nuclei in pristine tropical rainforest air of Amazonia: size-resolved measurements and modeling of atmospheric aerosol composition and CCN activity

Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. We have measured and characterized CCN at water vapor supersaturations in the range of S=0.10-0.82% in pristine tropical rainforest air during the AMAZE-08 campaign in central Amazonia. The effective hygroscopicity parameters describing the influence of chemical composition on the CCN activity of aerosol particles varied in the range of kappa approximate to 0.1-0.4 (0.16+/-0.06 arithmetic mean and standard deviation). The overall median value of kappa approximate to 0.15 was by a factor of two lower than the values typically observed for continental aerosols in other regions of the world. Aitken mode particles were less hygroscopic than accumulation mode particles (kappa approximate to 0.1 at D approximate to 50 nm; kappa approximate to 0.2 at D approximate to 200 nm), which is in agreement with earlier hygroscopicity tandem differential mobility analyzer (H-TDMA) studies. The CCN measurement results are consistent with aerosol mass spectrometry (AMS) data, showing that the organic mass fraction (f(org)) was on average as high as similar to 90% in the Aitken mode (D <= 100 nm) and decreased with increasing particle diameter in the accumulation mode (similar to 80% at D approximate to 200 nm). The kappa values exhibited a negative linear correlation with f(org) (R(2)=0.81), and extrapolation yielded the following effective hygroscopicity parameters for organic and inorganic particle components: kappa(org)approximate to 0.1 which can be regarded as the effective hygroscopicity of biogenic secondary organic aerosol (SOA) and kappa(inorg)approximate to 0.6 which is characteristic for ammonium sulfate and related salts. Both the size dependence and the temporal variability of effective particle hygroscopicity could be parameterized as a function of AMS-based organic and inorganic mass fractions (kappa(p)=kappa(org) x f(org)+kappa(inorg) x f(inorg)). The CCN number concentrations predicted with kappa(p) were in fair agreement with the measurement results (similar to 20% average deviation). The median CCN number concentrations at S=0.1-0.82% ranged from N(CCN,0.10)approximate to 35 cm(-3) to N(CCN,0.82)approximate to 160 cm(-3), the median concentration of aerosol particles larger than 30 nm was N(CN,30)approximate to 200 cm(-3), and the corresponding integral CCN efficiencies were in the range of N(CCN,0.10/NCN,30)approximate to 0.1 to N(CCN,0.82/NCN,30)approximate to 0.8. Although the number concentrations and hygroscopicity parameters were much lower in pristine rainforest air, the integral CCN efficiencies observed were similar to those in highly polluted megacity air. Moreover, model calculations of N(CCN,S) assuming an approximate global average value of kappa approximate to 0.3 for continental aerosols led to systematic overpredictions, but the average deviations exceeded similar to 50% only at low water vapor supersaturation (0.1%) and low particle number concentrations (<= 100 cm(-3)). Model calculations assuming aconstant aerosol size distribution led to higher average deviations at all investigated levels of supersaturation: similar to 60% for the campaign average distribution and similar to 1600% for a generic remote continental size distribution. These findings confirm earlier studies suggesting that aerosol particle number and size are the major predictors for the variability of the CCN concentration in continental boundary layer air, followed by particle composition and hygroscopicity as relatively minor modulators. Depending on the required and applicable level of detail, the information and parameterizations presented in this paper should enable efficient description of the CCN properties of pristine tropical rainforest aerosols of Amazonia in detailed process models as well as in large-scale atmospheric and climate models.

Polarization effects in molecular dynamics simulations of glass-formers Ca(NO(3))(2)center dot nH(2)O, n=4, 6, and 8

Thermodynamics, equilibrium structure, and dynamics of glass-forming liquids Ca(NO(3))(2)center dot nH(2)O, n=4, 6, and 8, have been investigated by molecular dynamics (MD) simulations. A polarizable model was considered for H(2)O and NO(3)- on the basis of previous fluctuating charge models for pure water and the molten salt 2Ca(NO(3))(2)center dot 3KNO(3). Similar thermodynamic properties have been obtained with nonpolarizable and polarizable models. The glass transition temperature, T(g), estimated from MD simulations was dependent on polarization, in particular the dependence of T(g) with electrolyte concentration. Significant polarization effects on equilibrium structure were observed in cation-cation, cation-anion, and water-water structures. Polarization increases the diffusion coefficient of H(2)O, but does not change significantly the diffusion coefficients of ions. Viscosity decreases upon inclusion of polarization, but the conductivity calculated with the polarizable model is smaller than the nonpolarizable model because polarization enhances anion-cation interactions.