A general and regioselective synthesis of cyclopentenone derivatives through nickel(0)-mediated [3 + 2] cyclization of alkenyl Fischer carbene complexes and internal alkynes

A broad range of substituted 2-cyclopentenone derivatives 3-6 are synthesized by the nickel(0)-mediated [3 + 2] cyclization reaction of chromium alkenyl(methoxy)carbene complexes 1 and internal alkynes 2. The reaction takes place with complete regioselectivity with both unactivated alkynes and activated alkynes (electron-withdrawing and electron-donating substituted alkynes). Representative cycloadducts containing boron and tin substituents are further demonstrated to be active partners in classical Pd-catalyzed C-C coupling processes to allow the production of 2-aryl- and 2-alkynyl-substituted cyclopentenones 9-13.     

Thalidomide analogs from diamines: Synthesis and evaluation as inhibitors of TNF-alpha production

Fourteen thalidomide analogs bearing two phthalimido units were prepared in high yields (83-94%) by condensation of different diamines with phthalic or 3-nitrophthalic anhydride. An in vitro investigation of the compounds as inhibitors of the TNF-alpha production was performed. The inhibition was higher for compounds bearing amino and nitro groups and was modulated by increasing the size of the spacers between the phthalimide groups.     

Aggregation and adsorption of reactive dyes in the presence of an anionic surfactant on mesoporous aminopropyl silica

A surface tension technique was used to determine the critical aggregation concentration (cac) of a yellow and a red dye in relation to the presence of the anionic surfactant sodium dodecylbenzene sulfonate (DBS) and to temperature changes in buffered aqueous solutions. The cac values of the yellow dye increase from 25 to 45 degrees C (from 41.37 to 50.32 mg L-1) and decrease from 45 to 55 degrees C (from 50.32 to 38.72 mg L-1). The cac values for the red dye/DBS aggregates decrease (from 124.52 to 88.50 mg L-1) from 25 to 55 degrees C. Adsorption of the two dyes onto a mesoporous aminopropyl silica (Sil-NH2) was also studied. The adsorption of the yellow dye increases with an increase in temperature from 25 to 55 degrees C. In the presence of DBS the adsorption on Sil-NH2 for the yellow dye decreases, and for the red dye increases from 25 to 55 degrees C. Adsorptions occurred below and above the cac of the anionic dyes/DBS aggregates. Adsorption of the dyes onto Sil-NH2 fitted well to the Langmuir, Freundlich, and Redlich-Peterson adsorption models. However, in the presence of DBS, only the Freundlich model fit the experimental adsorption data at low dye concentrations (less than 400 mg L-1). In this case, the Redlich-Peterson model was only fitted to the red dye adsorption data. The magnitude of the Dubinin-Radushkevich energetic parameters (E, from 7.00 to 15.00 kJ mol-1) indicates that the adsorption of the dyes onto Sil-NH2, in the absence and in the presence of DBS, is controlled by water adsorbed/dye in solution ion-exchange interactions. It is observed that the values of DeltaadsH are positive for both dyes and the values are quite similar to each other. The exception is the adsorption of the yellow dye in the presence of DBS, which is slightly exothermic. The DeltaadsG values are all negative. However, the interactions of the dyes with Sil-NH2 silica are more spontaneous in the presence of the surfactant. The positive adsorption entropy values (DeltaadsS) for the interaction of the dyes suggest that entropy is a driving force of the dye adsorptions. However, the entropic contribution is higher for the adsorptions in the presence of DBS. It was suggested that the chemical structures of the dyes play an important role in the formation of the dye/DBS aggregates and in dye adsorption onto the aminopropyl silica.     

Photo-induced destruction of giant vesicles in methylene blue solutions

We study the photodecomposition of phospholipid bilayers in aqueous solutions of methylene blue. Observation of giant unilamellar vesicles under an optical microscope reveals a consistent pattern of membrane disruption as a function of methylene blue concentration and photon density for different substrates supporting the vesicles.     

Solid-phase synthesis of novel trimers containing a phenylstatine core and analysis by high-resolution magic angle spinning

Here we describe a multistep solid-phase synthetic approach for the addition of amino acid residues to both the C- and N-termini of a phenylstatine core, yielding a library aimed at the development of structure-activity relationships in the S2 and S2' regions of the aspartyl proteases. Optimization of the synthetic strategy was performed on the basis of the in situ analysis of the compounds bound to the solid support through high-resolution magic angle spinning NMR Spectroscopy (HR-MAS NMR).     

A Categorical View to Structural Complexity

In the present work we are interested in to provide a universal language for supporting formalisms to specify the approximation hierarchy system for an abstract NP‐hard optimization problem. This work grew from the idea of providing a categorical view of structural complexity to optimization problems. The direction is aimed towards actually exploring the connections among the structural complexity aspects and categorical concepts, which may be viewed in a high‐level, in a structuralistic sense. After introducing the optimization problems categories OPTS and OPT, as well as related questions, a formal system modelling the approximation hierarchy of a given optimization problem is provided, based on categorical shape theory. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Physical-Mechanical Behavior and Water-Barrier Properties of Biopolymers-Clay Nanocomposites

The preparation and characterization of biodegradable films based on starch-PVA-nanoclay by solvent casting are reported in this study. The films were prepared with a relation of 3:2 of starch:PVA and nanoclay (0.5, 1.0, and 1.5% w/v), and glycerol as plasticizer. The nanoclays before being incorporated in the filmogenic solution of starch-PVA were dispersed in two ways: by magnetic stirring and by sonication. The SEM results suggest that the sonication of nanoclay is necessary to reach a good dispersion along the polymeric matrix. FTIR results of films with 1.0 and 1.5% w/v of sonicated nanoclay suggest a strong interaction of hydrogen bond with the polymeric matrix of starch-PVA. However, the properties of WVP, tensile strength, percentage of elongation at break, and Young’s modulus improved to the film with sonicated nanoclay at 0.5% w/v, while in films with 1.0 and 1.5% w/w these properties were even worse than in film without nanoclay. Nanoclay concentrations higher than 1.0 w/v saturate the polymer matrix, affecting the physicochemical properties. Accordingly, the successful incorporation of nanoclays at 0.5% w/v into the matrix starch-PVA suggests that this film is a good candidate for use as biodegradable packaging.     

In Situ Incorporation of Praziquantel in Polymer Microparticles through Suspension Polymerization for Treatment of Schistosomiasis

Schistosomiasis is one of the major public health problems worldwide. Even though this is a common illness among preschool children in poor countries, treatment is carried out mainly through the administration of praziquantel tablets, which has some disadvantages, such as the strong bitter taste. As an alternative to overcome this problem, the development of new encapsulated praziquantel formulations is demanded. For this reason, suspension polymerizations are carried out for the in situ encapsulation of praziquantel into polymer microparticles, using methyl methacrylate (MMA) and cationic compounds (diethylaminoethyl methacrylate, DEAEMA, and dimethylaminoethyl methacrylate, DMAEMA) as comonomers. This technique allows for the preparation of polymer microparticles with high encapsulation efficiencies (>90%) with characteristic sizes ranging from 0.5 to 1500 µm. Drug release profiles show that praziquantel is released from poly(methyl methacrylate) microparticles slowly due to the existence of strong diffusional resistance. On the other hand, the addition of cationic comonomers renders polymer particles sensitive to pH variations, allowing for faster release of praziquantel in acidic environments, as found in the stomach.     

Thermography Applied to the Study of Fatigue Crack Propagation in Polycarbonate

Thermography was used to study the propagation of fatigue cracks during cyclic loading of pre-cracked SAE keyhole polycarbonate specimens. A micro-bolometer infrared camera (FLIR A655sc) and a commercially available software program (DeltaTherm2) were employed. The stress intensity factors were determined using a hybrid thermoelastic stress analysis (TSA) technique. The crack growth rate was determined via thermography using two different approaches. The first approach used the output of the crack-tip position from the developed TSA algorithm and the number of cycles between data sets. The second approach used temperature measurement as a new way to determine da/dN (crack growth rate) directly. As a result, da/dN vs ΔK (stress intensity factor range) graphs were plotted and fitted using Paris’ law. A comparison between the resultant da/dN vs ΔK curves and results found in the literature, as well as curves from the finite element method (FEM) simulations showed good agreement. The conclusion was that thermography is a very powerful tool that can detect, measure and monitor fatigue cracks in polycarbonate.     

Identification of potential trypanothione reductase inhibitors among commercially available $$\upbeta $$-carboline derivatives using chemical space,lead-like and drug-like filters,pharmacophore models and molecular docking

American trypanosomiasis or Chagas disease caused by the protozoan Trypanosoma cruzi (T. cruzi) is an important endemic trypanosomiasis in Central and South America. This disease was considered to be a priority in the global plan to combat neglected tropical diseases, 2008–2015, which indicates that there is an urgent need to develop more effective drugs. The development of new chemotherapeutic agents against Chagas disease can be related to an important biochemical feature of T. cruzi: its redox defense system. This system is based on trypanothione (\(N^{1}\),\(N^{8}\)-bis(glutathyonil)spermidine) and trypanothione reductase (TR), which are rather unique to trypanosomes and completely absent in mammalian cells. In this regard, tricyclic compounds have been studied extensively due to their ability to inhibit the T. cruzi TR. However, synthetic derivatives of natural products, such as \(\upbeta \)-carboline derivatives (\(\upbeta \)-CDs), as potential TR inhibitors, has received little attention. This study presents an analysis of the structural and physicochemical properties of commercially available \(\upbeta \)-CDs in relation to compounds tested against T. cruzi in previously reported enzymatic assays and shows that \(\upbeta \)-CDs cover chemical space that has not been considered for the design of TR inhibitors. Moreover, this study presents a ligand-based approach to discover potential TR inhibitors among commercially available \(\upbeta \)-CDs, which could lead to the generation of promising \(\upbeta \)-CD candidates.