A Ring Contraction Strategy toward a Diastereoselective Total Synthesis of (+)-Bakkenolide A

A diastereoselective route to (+)-bakkenolide A is presented from the readily available optically active Wieland-Miescher ketone. This novel synthesis of this sesquiterpene lactone features the following as key stereoselective transformations: (i) the ring contraction reaction of a octalone mediated by thallium(III) nitrate (TTN); (ii) a hydrogenation to create the cis-fused junction; and (iii) the formation of the C7 quaternary center through an enolate intermediate. Furthermore, during this work, the absolute configuration of a trinorsesquiterpene isolated from Senecio Humillimus was assigned.

Electrostatic layer-by-layer deposition and electrochemical characterization of thin films composed of MnO(2) nanoparticles in a room-temperature ionic liquid

Thin films of MnO(2) nanoparticles were grown using the layer-by-layer method with poly (diallyldimetylammonium) as the intercalated layer. The film growth was followed by UV-vis, electrochemical quartz crystal microbalance (EQCM), and atomic force microscopy. Linear growth due to electrostatic immobilization of layers was observed up to 30 bilayers, but electrical connectivity was maintained only for 12 MnO(2)/PPDA bilayers. The electrochemical characterization of this film in 1-butyl-2,3-dimethyl-imidazolium (BMMI) bis(trifluoromethanesulfonyl)imide (TFSI) (BMMITFSI) with and without addition of a lithium salt indicated a higher electrochemical response of the nanostructured electrode in the lithium-containing electrolyte. On the basis of EQCM experiments, it was possible to confirm that the charge compensation process is achieved mainly by the TFSI anion at short times (<2 s) and by BMMI and lithium cations at longer times. The fact that large ions like TFSI and BMMI participate in the electroneutrality is attributed to the redox reaction that occurs at the superficial sites and to the high concentration of these species compared to that of lithium cations.

Surface active ionic liquids: Study of the micellar properties of 1-(1-alkyl)-3-methylimidazolium chlorides and comparison with structurally related surfactants

The impetus for the increasing interest in studying surface active ionic liquids (SAILs; ionic liquids with long-chain ""tails"") is the enormous potential for their applications, e.g., in nanotechnology and biomedicine. The progress in these fields rests on understanding the relationship between surfactant structure and solution properties, hence applications. This need has prompted us to extend our previous study on 1-(1-hexadecyl)-3-methylimidazolium chloride to 1-(1-alkyl)-3-methylimidazolium chlorides, with alkyl chains containing 10, 12, and 14 carbons. In addition to investigating relevant micellar properties, we have compared the solution properties of the imidazolium-based surfactants with: 1-(1-alkyl)pyridinium chlorides, and benzyl (2-acylaminoethyl)dimethylammonium chlorides. The former series carries a heterocyclic ring head-group, but does not possess a hydrogen that is as acidic as H2 of the imidazolium ring. The latter series carries an aromatic ring, a quaternary nitrogen and (a hydrogen-bond forming) amide group. The properties of the imidazolium and pyridinium surfactants were determined in the temperature range from 15 to 75 degrees C. The techniques employed were conductivity, isothermal titration calorimetry, and static light scattering. The results showed the important effects of the interactions in the interfacial region on the micellar properties over the temperature range studied. (C) 2011 Elsevier Inc. All rights reserved.

Catalytic Enantioselective alpha-Arylation of Carbonyl Compounds

Enantioselective creation of benzylic quaternary centers still is a continuous challenge to many synthetic organic chemists. Among the existing methods for installation of this type of center, the direct asymmetric alpha-arylation of carbonyl compounds is very attractive due to the ready availability of the coupling substrates. Herein, we present some new tools to the catalytic asymmetric alpha-arylation of carbonyl compounds that overcame many of the drawbacks posted in previous methods for this type of reaction.

Expression, purification and kinetic characterization of His-tagged glyceraldehyde-3-phosphate dehydrogenase from Trypanosoma cruzi

Trypanosomes are flagellated protozoa responsible for serious parasitic diseases that have been classified by the World Health Organization as tropical sicknesses of major importance. One important drug target receiving considerable attention is the enzyme glyceraldehyde-3-phosphate dehydrogenase from the protozoan parasite Trypanosoma cruzi, the causative agent of Chagas disease (T. cruzi Glyceraldehyde-3-phosphate dehydrogenase (TcGAPDH); EC 1.2.1.12). TcGAPDH is a key enzyme in the glycolytic pathway of T. cruzi and catalyzes the oxidative phosphorylation of D-glyceraldehyde-3-phosphate (G3P) to 1,3-bisphosphoglycerate (1,3-BPG) coupled to the reduction of oxidized nicotinamide adenine dinucleotide, (NAD(+)) to NADH, the reduced form. Herein, we describe the cloning of the T. cruzi gene for TcGAPDH into the pET-28a(+) vector, its expression as a tagged protein in Escherichia coli, purification and kinetic characterization. The His(6)-tagged TcGAPDH was purified by affinity chromatography. Enzyme activity assays for the recombinant His(6)-TcGAPDH were carried out spectrophotometrically to determine the kinetic parameters. The apparent Michaelis-Menten constant (K(M)(app)) determined for D-glyceraldehyde-3-phosphate and NAD(+) were 352 +/- 21 and 272 +/- 25 mu M, respectively, which were consistent with the values for the untagged enzyme reported in the literature. We have demonstrated by the use of Isothermal Titration Calorimetry (ITC) that this vector modification resulted in activity preserved for a higher period. We also report here the use of response surface methodology (RSM) to determine the region of optimal conditions for enzyme activity. A quadratic model was developed by RSM to describe the enzyme activity in terms of pH and temperature as independent variables. According to the RMS contour plots and variance analysis, the maximum enzyme activity was at 29.1 degrees C and pH 8.6. Above 37 degrees C, the enzyme activity starts to fall, which may be related to previous reports that the quaternary structure begins a process of disassembly. (C) 2010 Elsevier Inc. All rights reserved.

The Molecular Chaperone Hsp70 Family Members Function by a Bidirectional Heterotrophic Allosteric Mechanism

The Hsp70 family is one of the most important and conserved molecular chaperone families. It is well documented that Hsp70 family members assist many cellular processes involving protein quality control, as follows: protein folding, transport through membranes, protein degradation, escape from aggregation, intracellular signaling, among several others. The Hsp70 proteins act as a cellular pivot capable of receiving and distributing substrates among the other molecular chaperone families. Despite the high identity of the Hsp70 proteins, there are several homologue Hsp70 members that do not have the same role in the cell, which allow them to develop and participate in such large number of activities. The Hsp70 proteins are composed of two main domains: one that binds ATP and hydrolyses it to ADP and another which directly interacts with substrates. These domains present bidirectional heterotrophic allosteric regulation allowing a fine regulated cycle of substrate binding and release. The general mechanism of the Hsp70s cycle is under the control of ATP hydrolysis that modulates the low (ATP-bound state) and high (ADP-bound state) affinity states of Hsp70 for substrates. An important feature of the Hsp70s cycle is that they have several co-chaperones that modulate their cycle and that can also interact and select substrates. Here, we review some known details of the bidirectional heterotrophic allosteric mechanism and other important features for Hsp70s regulating cycle and function.

"Falun ovan från Falun under", ny kunskap om Falu gruva. Projektrapport 2 : Jordartskartering och sedimentborrningar runt Falu gruva

This report is the second presentation of the project ‘Falun above from Falun under’ and comprises one report on ongoing work within the project. The main aims of this particular project are to reconstruct the landscape surrounding Falu Copper mine before mining activity started and to determine how increasing activity in the area affected the environment, and whether this could be measured as an indicator of increasing human impact in the area. This report presents the mapping and investigation of quaternary deposits and landscape analysis, the results from cores taken at two lake sites, Önsbacksdammen and Stora Vällan, 14C dating on selected seeds, and planning of continued research within the project.

Field report from sediment coring in peat for landscape analysis in Hjaltadalur, Skagafjörður, north Iceland 2010 : Sediment drilling in Hólar, Vidvik and Kolkuós, Hjaltadalur

This field report presents fieldwork undertaken in Hjaltadalur, Skagafjördur, northern Iceland during summer 2010. The main aim was to initiate coring in selected mires in order to determine the composition of organic material and sediments in the mires, sub-sample for sedimentological and palaeoecological analyses, and initiate advanced landscape analysis of Hjaltadalur. Three mires were selected for sediments coring in Hjaltadalur: Ástunga close to Kolkóus, Hólakot at Viðvik, and Hólar. All three represented a landscape transect in NW to SE direction, from close to the coast to valley interior, i.e. close to the old settlement at Hólar.

Em busca de um padrão de atendimento: O caso da secretaria da escola de pós-graduação em economia (EPGE) da Fundação Getulio Vargas (FGV)

This work has as its objective to create a service¿s pattern to EPGE Secretary, so we can solve the endless stress of the quaternary sector organization, where teachers and secretary professionals just can¿t get along. This systemic model intends to create a definite solution to that problem, allowing teachers to dedicate their time only to research and orientation to students. That way, we can keep the high quality of the secretary¿s service, as we are the symbol of EPGE through the eyes of the public. Having done the theoretical conceptualization of Organizations, Systems and Methods and also Geertz Theory of Ethnography, we build a pattern system, adapted to FGV¿s secretaries cultural situation. A group of 21 professionals from FGV¿s secretaries was selected and through a qualitative research, it was sustained the six years field work of the thesis author. The group¿s contribution to this work was fundamental to build the model and can also create a new way of thinking the work from secretaries of FGV.

ESR dating of pleistocene mammal teeth and its implications for the biostratigraphy and geological evolution of the coastal plain, Rio Grande do Sul, southern Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Eça de Queiroz e a cozinha burguesa: literatura e alimentação

Using literature to discuss the topic of food, proper bourgeois cuisine, was the purpose of this work. As a corpus, we use one of the works of Eça de Queiroz, The City and the Mountains. Served as theoretical references the Claude Levi-Strauss s concept of universal culinary and the Jean Claude Fischler s concept of specific culinary who understands food as a cultural system which includes representations, beliefs and practices of a specific group. After the initial reading of the novel and construction of a file containing general information of the work, categories designed for elaboration of a material for analysis were these: work, characters, food, intellectuals and geographies. We realized the culinary as an epicenter for understanding the culture of a specific group: in this case, the bourgeois. We proposed a quaternary model for systematizing it: this bourgeois cuisine highlights the technique, has affection for what is rare and/or expensive but still consume it with temperance, establishing a new relationship with the use of time and, finally, it is the one that opens the ritual that involves frequent restaurants and cafes. The exercise of thinking the bourgeois cuisine through the literature suggests that the art may work on increase the comprehensive capabilities of nutritionists, professionals who deal with a complex object in your practice: the food

Compreensão de natureza e formação do biólogo

Most knowledge and techniques developed by mankind since ancient times had the main purpose to study and understand the various phenomena of Nature. Science, like one of these narratives, works as a translation, transcribing what, is systematically observed. Within the set of transformations on the modern sciences, the dialogue with related areas became quite narrow and, occasionally, functional, and the dialogue with non-related areas, in turn, does not takes place by any matters. The focus of this research is the teaching of Biological Sciences, and the undergraduate courses as strategic places to disseminate a broad understanding of Nature, that broadens the conceptual relations between different disciplinary axes, previously fragmented. In order to do so, I take a four-way metaphorical approach as a methodological construction base. Three of them proposed by Joël de Rosnay, represented by artifacts: The Telescope, The Microscope and the Macroscope. And finally, a proposition that complements the approach, that i named The Naked Eye. In Telescope, which allows a more general construct of a phenomenon, I discuss the teaching of Biological Sciences in Brazil. In the microscope, which allows us to analyze in detail a scenario, I construct a rank of the major courses in biological sciences and propose a discussion on the understanding of nature on the undergraduate programs. In Macroscope, who allows, at the same time, zoom in and out to the phenomenon observed, I call for a transdisciplinary dialogue, based on the authors Ilya Prigogine, Basarab Nicolescu, Henri Atlan and Bruno Latour, which can certainly contribute to the curriculum of the Biologists training programs, that builds knowledge pertinent to a complex observation of Nature. I complete the set of the quaternary reading and understanding of the world from the Naked Eye, as the first strategy of perception in our species. For this, I invite the philosopher of Nature Chico Lucas da Silva as my interlocutor

Flotação por ar dissolvido para os minerais quartzo e feldspato utilizando coletores catiônicos

The pegmatite rocks in Rio Grande do Norte are responsible for much of the production of industrial minerals like quartz and feldspar. Quartz and feldspar are minerals from pegmatite which may occur in pockets with metric to centimetric dimensions or as millimetric to sub millimetric intergrowths. The correct physical liberation of the mineral of interest, in case of intergrowths, requires an appropriate particle size, acquired by size reduction operations. The method for treating mineral which has a high efficiency fines particles recovery is flotation. The main purpose of the present study is to evaluate the recovery of quartz and potassium feldspar using cationic diamine and quaternary ammonium salt as collectors by means of dissolved air flotation DAF. The tests were performed based on a central composite design 24, by which the influence of process variables was statistically verified: concentration of the quaternary ammonium salt and diamine collectors, pH and conditioning time. The efficiency of flotation was calculated from the removal of turbidity of the solution. Results of maximum flotation efficiency (60%) were found in the level curves, plotted in conditions of low concentrations of collectors (1,0 x 10-5 mol.L-1). These high flotation efficiencies were obtained when operating at pH 4 to 8 with conditioning time ranging from 3 to 5 minutes. Thus, the results showed that the process variables have played important roles in the dissolved air flotation process concerning the flotability of the minerals.

Activity of disinfectants against foodborne pathogens in suspension and adhered to stainless steel surfaces

The purpose of this study was to investigate and compare the efficacy of various disinfectants on planktonic cells and biofilm cells of Listeria monocytogenes, Staphylococcus aureus and Escherichia coli. Numbers of viable biofilm cells decreased after treatment with all tested disinfectants (iodine, biguanide, quaternary ammonium compounds, peracetic acid and sodium hypochlorite). Sodium hypochlorite was the most effective disinfectant against biofilm cells, while biguanide was the least effective. Scanning electron microscopy observations revealed that cells adhered on stainless steel surface after treatment with the disinfectants. No viable planktonic cells were observed after treatment with the same disinfectants. Based on our findings, we concluded that biofilm cells might be more resistant to disinfectants than plancktonic cells.