Copper catalyzed cross-coupling reactions of diaryl ditellurides with potassium aryltrifluoroborate salts

We present here results of the cross-coupling reaction of diaryl ditellurides with potassium aryltrifluoroborate salts using a catalytic amount of Cu(OAc)2 and bypiridine in DMSO/H2O under air atmosphere. This cross-coupling reaction is general and was performed with diaryl ditellurides and potassium aryltrifluoroborate salts bearing electron-withdrawing, electron-donating and neutral substituents, affording the corresponding unsymmetrical diaryl tellurides in good to excellent yields.Apresentamos aqui resultados das reações de acoplamento de diteluretos de diarila com sais de ariltrifluoroborato de potássio, usando quantidades catalíticas de Cu(OAc)2 e bipiridina, em uma mistura de DMSO/H2O, sob ar atmosférico. Estas reações de acoplamento são gerais e são realizadas com diteluretos de diarila e sais de ariltrifluoroborato de potássio contendo substituintes neutros, retiradores e doadores de elétrons, fornecendo os correspondentes teluretos de diarila não simétricos em rendimentos de bons a excelentes.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) (Grants 07/56659-0 and 07/59404-2

2-chlorovinyl tellurium dihalides, (p-tol)Te[C(H)=C(Cl)Ph]X2 for X = Cl, Br and I: variable coordination environments, supramolecular structures and docking studies in cathepsin B

Crystallography shows that the Te atom in each of (p-tol)Te[C(H)=C(Cl)Ph]X2, for X = Cl (1), Br (2) and I (3), is within a distorted Ψ-pentagonal bipyramidal geometry. An E configuration for the vinyl group in (1) precludes the formation of an intramolecular Te···Cl interaction so that an intramolecular Te···π interaction is found instead. The coordination environment features a linear Cl-Te-Cl arrangement with the pentagonal plane defined by the two C atoms of the organic substituents, an intermolecular Te···Cl contact, a Te···π interaction and a stereochemically active lone pair of electrons. In the X = Br (2) and I (3) structures, similar coordination geometries are found but the Te···π contact is replaced by an intramolecular Te···Cl contact owing to the adoption of a Z configuration about the vinyl bond. The differences in structure are readily explained in terms of electronic effects. Docking studies of cathepsin B with (1')-(3'), i.e. 1-3 less one Te-bound halide, show efficient binding through the agency of covalent Te-S Cys29 bonds with stabilization afforded by a combination of N-H···π, C-H···π and Cl vinyl···H interactions. These results comparable favorably with known inhibitors of cathepsin B suggesting the title compounds have potential biological activity.Os estudos cristalográficos mostram que o poliedro de coordenação ao redor do átomo de Te, em cada um dos compostos (p-tol)Te[C(H)=C(Cl)Ph]X2, com X = Cl (1), Br (2) e I (3), é uma Ψ-bipirâmide pentagonal distorcida. O grupo vinil em (1) adota uma configuração E o que impede a formação de uma interação intramolecular Te···Cl e em seu lugar é encontrada uma interação intramolecular Te···π. O poliedro de coordenação é formado por um arranjo linear Cl-Te-Cl com o plano pentagonal definido por dois átomos de C dos substituintes orgânicos, um contato intermolecular Te···Cl, uma interação Te···π e um par isolado de elétrons estereoquimicamente ativo. Geometrias de coordenação semelhantes são encontradas para as estruturas com X = Br (2) e I (3), mas a interação π é substituída por uma interação intramolecular Te···Cl devido à adoção de uma configuração Z em torno da ligação vinil. As diferenças nas estruturas são facilmente explicadas em termos de efeitos eletrônicos. Estudos de docking em catepsina B com (1')-(3'), ou seja, compostos 1 a 3 em que há um haleto a menos ligado ao átomo de Te, mostram que há uma ligação eficiente com a proteína pela formação da ligação covalente Te-S Cys29 com a estabilização proporcionada por uma combinação de interações N-H···π, C-H···π e Cl vinyl···H. Estes resultados são comparáveis aos obtidos com inibidores conhecidos da catepsina B o que sugere que os compostos estudados têm potencial atividade biológica.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Universidade Federal de São Carlos Departamento de FísicaUniversidade Federal de São Carlos Departamento de Química Laboratório de Cristalografia, Estereodinâmica e Modelagem MolecularUniversidade de São Paulo Faculdade de Ciências Farmacêuticas Departamento de FarmáciaUniversidade Federal de São Paulo (UNIFESP) Departamento de QuímicaUniversity of Malaya Department of ChemistryUNIFESP, Depto. de QuímicaFAPESP: 07/59404-2CNPq: 300613/2007CNPq: 306532/2009-3CNPq: 140925/2009-0CAPES: 808/2009SciEL

Preparado do solo, erosao hídrica, e perdas de cálcio, magnésio e carbono orgânico

[Abstract] Soil tillage influences water erosion, and consequently, losses of calcium, magnesium and organic carbon in surface runoff. Nutrients and organic carbon are transported by surface runoff in particulate form, adsorbed to soil colloids or soluble in water, depending on the soil tillage system. This study was carried out on an Inceptisol, representative of the Santa Catarina highlands, southern Brazil, between November 1999 and October 2001, under natural rainfall. The soil tillage treatments (no replications) were: no-tillage (NT), minimum soil tillage with chiseling + disking (MT), and conventional soil tillage with plowing + two diskings (CT). The crop cycles sequence was soybean (Glycine max), oats (Avena sativa), beans (Phaseolus vulgaris) and vetch (Vicia sativa). Conventional soil tillage treatment with plowing + two disking in the absence of crops (BS) was also studied. Calcium and magnesium concentrations were determined in both water and sediments of the surface runoff, while organic carbon was measured only in sediments. Calcium and magnesium concentrations were greater in sediments than in surface runoff, while total losses of these elements were greater in surface runoff than in sediments. The greatest calcium and magnesium concentrations in surface runoff were obtained under CT, while in sediments the greatest concentration occurred under MT. Organic carbon concentration in sediments did not differ under the different soil tillage systems, and the greatest total loss was under CT system

Crystallographic, DFT and docking (cathepsin B) studies on an organotellurium(IV) compound

Some biologically active organotellurium compounds exhibit inhibitory potency against cathepsin B. In this study, an alkyl derivative, viz. [CH3(CH2)2C(I)=C(H)](nBu)TeI2, 1, has been structurally characterised by X-ray crystallography and shown to be coordinated within a C2I2 donor set. When the stereochemically active lone pair of electrons is taken into account, a distorted trigonal bipyramidal geometry results with the iodide atoms in axial positions. Both intra- and inter-molecular Te···I interactions are also noted. If all interactions are considered, the coordination geometry is based on a Ψ-pentagonal bipyramidal geometry. An unusual feature of the structure is the curving of the functionalised C5 chain. This feature has been explored by DFT methods and shown to arise as a result of close C–H···I interactions. A docking study (cathepsin B) was performed to understand the inhibition mechanism and to compare the new results with previous observations. Notably, 1 has the same pose exhibited by analogous biologically active compounds with aryl groups. Thus, the present study suggests that (alkyl)2TeX2 compounds should also be evaluated for biological activity

Nutritional value of canola expellers produced "on farm" by cold extraction of oil used as bio fuel

General aim of this thesis was to study canola expellers (CE) extracted by cold pressing in a small plant (on farm) and to evaluate the validity to use this by-product in ruminant feeding. The thesis includes the results of four experimental contributes: the first one aimed to evaluate the stability of CE at different times and temperatures of storage in order to determine if the conditions usually found in the farms, especially during the hot season, can result in changes in fatty acids profile and in some oxidative parameters. Results found that under different temperatures (12, 24, and 36°C) and times of storage (10, 20, and 30 d), CE maintained a good oxidative stability, as evidenced by low peroxide values (< 10 mEq/kg fat) in all samples collected, by negative response for Kreis test and by low changes in fatty acids profile. From these results it could be hypothesized that the storage of these by-products did not change the characteristics of the lipid fraction. In the second contribute in vitro gas production (GP) values obtained from the incubation of CE, whole soybean seed (WSS) and soybean meal (SBM) were compared, incubating feed samples with two media containing N-rich buffer or N-free buffer, in order to compare the effect of the availability of feed as unique protein source. Results of the experiment showed that CE is an easily degradable protein source. In the first hours of incubation with limiting N availability, higher gas production was recorded compared to the two soybeans. On this basis, CE could be interesting in diets at low protein content, currently suggested in order to reduce nitrogen excretion. No toxic effects on the microbial yield were observed during the fermentation of the three different feeds. The third contribute compared four diets formulated for beef cattle, based on corn silage and containing WSS or CE as protein sources at two different inclusion levels, in order to obtain 15 and 11 % CP of DM in the diets. Diets were tested using Rusitec fermenter. Compared to WSS, CE provided greater NDF degradability (P < 0.01), produced less acetate and propionate (P < 0.001) but more butyrate and branched-chain VFA. The total VFA production was similar for the two protein sources. With regard to nitrogen balance, CE showed greater 15N enrichment in the non-ammonia N (P < 0.01) and nominally lower values of microbial N derived from ammonia compared to WSS (P = 0.06). At high inclusion level, the 15N enrichments for ammonia N, non-ammonia N and total bacteria N were also greater than observed at low inclusion levels (P < 0.001). In conclusion, the two feeds showed different fermentation patterns. The manipulation of dietary protein level seemed to lead primarily to a variation of bypass protein, without effects on the synthesis of microbial N. In the fourth contribute the same diets tested in Rusitec fermenter (third contribute) were evaluated using RF system (Ankom Technology, Macedon, NY, USA) in order to evaluate their gas production kinetics. Results showed that both NDFd and TDMd values were greater (P<0.05) for CE diets compared to WSS, confirming the results obtained with Rusitec and as expected were lower (P=0.04) for L compared to H diets. Compared to WSS, CE inclusion in the diets increased the rate of GP (P<0.05;) but did not affect the total amount of GP. The reduction of CP level in the diets from 15 to 11% decreased the rate of GP without effects on total GP. Ammonia content increased (P<0.01), as expected, with the level of dietary CP. In conclusion, when diets with low CE levels are used, the inclusion of rapeseed cake in replacement to soybean seeds could improve the rate of degradation during the first hours of fermentation. In general CE obtained by cold extraction on farm could be an interesting feed in ruminant feeding with economical and environmental benefits

Recomendação de variedades de milho para o Sul do Brasil: rede de ensaios preliminares-Safra 2009/10.

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Mensuración de área de úlceras por presión por medio de los programas informáticos Motic y AutoCAD

A úlcera por pressão e uma lesão parcial ou total das camadas da pele em determinadas regiões do corpo e seu processo de cicatrização pode ser acompanhado por meio de processamento de imagens. A analise da área da ulcera por pressão e relevante para avaliação da sua evolução e de sua resposta a procedimentos terapeuticos. Os softwares Motic e AutoCADR permitem avaliar a área de regiões de uma imagem através da marcação do seu contorno. Valendo-se dessa técnica, 35 voluntários determinaram as áreas de duas ulceras por pressão grau III pelos dois tipos de software. Concluiu-se que eles apresentam resultados clinicamente concordantes e podem assim ser utilizados para acompanhamento da evolução da cicatrização de ulceras por pressão. _________________________________________________________________________________ ABSTRACTPressure ulcer is a lesion that affects skin layers in some regions of the body and its healing can be followed up using image processing. The analysis of pressure ulcer area is relevant to evaluate its evolution and response to therapeutic procedures. Such areas can be evaluated through contour marking with the softwares Motic and AutoCAD®. In this study 35 volunteers computed areas from two grade III pressure ulcers using these instruments. It was possible to conclude that results are clinically equivalent and so can be considered to follow up healing evolution from pressure ulcers. _________________________________________________________________________________ RESUMENÚlcera por presión es una lesión parcial o total de las capas de la piel en determinadas regiones del cuerpo y su cicatrización puede ser acompañada por el procesamiento de imágenes. El análisis de área de la úlcera por presión es pertinente para evaluar su evolución y respuesta a procedimientos terapéuticos. Los programas informáticos Motic y AutoCAD® permiten evaluar la área de una imagen por medio de la delimitación de su circunferencia. Con esta técnica, 35 voluntarios determinaron las áreas de dos ulceras por presión de grado III en los dos programas informáticos. Se concluye que ellos presentan resultados clínicamente concordantes y pueden ser utilizados para el acompañamiento de la evolución de la cicatrización de las úlceras por presión

Ensaio Regional de Variedades de Milho na Região Sul - Safra 2011/2012.

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