On the search for potential anti-Trypanosoma cruzi drugs: Synthesis and biological evaluation of 2-hydroxy-3-methylamino and 1,2,3-triazolic naphthoquinoidal compounds obtained by click chemistry reactions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Vegetable Oil Derived Solvent, and Catalyst Free Click Chemistry'' Thermoplastic Polytriazoles

Azide-alkyne Huisgen click chemistry provides new synthetic routes for making thermoplastic polytriazole polymers-without solvent or catalyst. This method was used to polymerize three diester dialkyne monomers with a lipid derived 18 carbon diazide to produce a series of polymers (labelled C18C18, C18C9, and C18C4 based on monomer chain lengths) free of residual solvent and catalyst. Three diester dialkyne monomers were synthesized with ester chain lengths of 4, 9, and 18 carbons from renewable sources. Significant differences in thermal and mechanical properties were observed between C18C9 and the two other polymers. C18C9 presented a lower melting temperature, higher elongation at break, and reduced Young's modulus compared to C18C4 and C18C18. This was due to the odd-even effect induced by the number of carbon atoms in the monomers which resulted in orientation of the ester linkages of C18C9 in the same direction, thereby reducing hydrogen bonding. The thermoplastic polytriazoles presented are novel polymers derived from vegetable oil with favourable mechanical and thermal properties suitable for a large range of applications where no residual solvent or catalyst can be tolerated. Their added potential biocompatibility and biodegradability make them ideal for applications in the medical and pharmaceutical industries.

Increase of leishmanicidal and tubercular activities using steroids linked to aminoquinoline

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Pyrearinus termitilluminans larval click beetle luciferase: Active site properties, structure and function relationships and comparison with other beetle luciferases

Several beetle luciferases have been cloned and sequenced. However, most studies on structure and function relationships and bioanalytical applications were done with firefly luciferases, which are pH sensitive. Several years ago we cloned Pyrearinus termitilluminans larval click beetle luciferase, which displays the most blue-shifted bioluminescence among beetle luciferases and is pH insensitive. This enzyme was expressed in E. coli, purified, and its properties investigated. This luciferase shows slower luminescence kinetics, KM values comparable to other beetle luciferases and high catalytic constant. Fluorescence studies with 8-anilino-1-naphtalene-sulfonic acid (1,8-ANS) and modeling studies suggest that the luciferin binding site of this luciferase is very hydrophobic, supporting the solvent and orientation polarizability effects as determining mechanisms for bioluminescence colors. Although pH insensitive in the range between pH 6-8, at pH 10 this luciferase displays a remarkable red-shift and broadening of the bioluminescence spectrum. Modeling studies suggest that the residue C312 may play an important role in bioluminescence color modulation. Compared to other beetle luciferases, Pyrearinus termitilluminans luciferase also displays higher thermostability and sustained luminescence in a bacterial cell environment, which makes this luciferase particularly suitable for in vivo cell analysis and bioimaging. © The Royal Society of Chemistry and Owner Societies 2009.

Recent Insights on the Medicinal Chemistry of Sickle Cell Disease

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Improvement of electrical properties of Sr-modified (Pb,Ca)TiO3 thin films grown by soft chemistry route

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Cellulose pyrolysis and quantum chemistry

Cellulose is the major constituent of most plants of interest as renewable sources of energy and is the most extensively studied form of biomass or biomass constituent. Predicting the mass loss and product yields when cellulose is subjected to increased temperature represents a fundamental problem in the thermal release of biomass energy. Unfortunately, at this time, there is no internally consistent model of cellulose pyrolysis that can organize the varied experimental data now available or provide a guide for additional experiments. Here, we present a model of direct cellulose pyrolysis using a multistage decay scheme that we first presented in the IJQC in 1984. This decay scheme can, with the help of an inverse method of assigning reaction rates, provide a reasonable account of the direct fast pyrolysis yield measurements. The model is suggestive of dissociation states of d-glucose (C6H10O5,), the fundamental cellulose monomer. The model raises the question as to whether quantum chemistry could now provide the dissociation energies for the principal breakup modes of glucose into C-1, C-2, C-3, C-4, and C-5 compounds. These calculations would help in achieving a more fundamental description of volatile generation from cellulose pyrolysis and could serve as a guide for treating hemicellulose and lignin, the other major biomass constituents. Such advances could lead to the development of a predictive science of biomass pyrolysis that would facilitate the design of liquifiers and gasifiers based upon renewable feedstocks. (C) 1998 John Wiley & Sons, Inc.

On the dynamic behaviour of the "click" mechanism in dipteran flight

In this paper, the dynamic behaviour of the "click" mechanism is analysed. A more accurate model is used than in the past, in which the limits of movement due to the geometry of the flight mechanism are imposed. Moreover, the effects of different damping models are investigated. In previous work, the damping model was assumed to be of the linear viscous type for simplicity, but it is likely that the damping due to drag forces is nonlinear. Accordingly, a model of damping in which the damping force is proportional to the square of the velocity is used, and the results are compared with the simpler model of linear viscous damping. Because of the complexity of the model an analytical approach is not possible so the problem has been cast in terms of non-dimensional variables and solved numerically. The peak kinetic energy of the wing root per energy input in one cycle is chosen to study the effectiveness of the "click" mechanism compared with a linear resonant mechanism. It is shown that, the "click" mechanism has distinct advantages when it is driven below its resonant frequency. When the damping is quadratic, there are some further advantages compared to when the damping is linear and viscous, provided that the amplitude of the excitation force is large enough to avoid the erratic behaviour of the mechanism that occurs for small forces. (C) 2011 Elsevier Ltd. All rights reserved.

Influence of thermal annealing treatment in oxygen atmosphere on grain boundary chemistry and non-ohmic properties of SnO2 center dot MnO polycrystalline semiconductors

The present work studied the influence of thermal treatment in oxygen rich atmosphere on heterogenous junctions in Mn-doped SnO2 polycrystalline system presenting varistor behavior. The samples were prepared by conventional oxide mixture methodology, and were submitted to heat treatment in oxygen rich atmosphere at 900 degrees C for 2h. The samples were characterized by X-ray diffraction, scanning electron microscopy, dc and ac electrical measurements. The results showed that there is an evident relationship between the microstructure heterogeneity and non-ohmic electrical properties. It was found that for this SnO2 center dot MnO-based varistor system the heat treatment in oxygen rich atmosphere does not necessarily increase the varistors properties, which was related to the decrease in the grain boundary resistance. The results are compared with Co-doped SnO2 varistors and ZnO based varistors. (C) 2008 WILEY-VCH Verlay GmbH & Co. KGaA, Weinheim.

Snake venom phospholipase A(2) inhibitors: Medicinal chemistry and therapeutic potential

Phospholipases A(2) (PLA(2)s) are commonly found in snake venoms from Viperidae, Hydrophidae and Elaphidae families and have been extensively studied due to their pharmacological and physiopathological effects in living organisms. This article reports a review on natural and artificial inhibitors of enzymatic, toxic and pharmacological effects induced by snake venom PLA(2)s. These inhibitors act on PLA(2)S through different mechanisms, most of them still not completely understood, including binding to specific domains, denaturation, modification of specific amino acid residues and others. Several substances have been evaluated regarding their effects against snake venoms and isolated toxins, including plant extracts and compounds from marine animals, mammals and snakes serum plasma, in addition to poly or monoclonal antibodies and several synthetic molecules. Research involving these inhibitors may be useful to understand the mechanism of action of PLA(2)s and their role in envenomations caused by snake bite. Furthermore, the biotechnological potential of PLA(2) inhibitors may provide therapeutic molecular models with antiophidian activity to supplement the conventional serum therapy against these multifunctional enzymes.

Mercury Redox Chemistry in the Negro River Basin, Amazon: The Role of Organic Matter and Solar Light

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Podzolization as a deferralitization process: dynamics and chemistry of ground and surface waters in an Acrisol-Podzol sequence of the upper Amazon Basin

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Ferroelectric and dielectric behaviour of Bi0.92La0.08FeO3 multiferroic thin films prepared by soft chemistry route

Bi0.92La0.08FeO3 (BLFO) thin films were grown on platine substrates by the soft chemical route. Ferroelectric and dielectric behaviors of BLFO films deposited by spin-coating technique and annealed at 773 K for 2 h in air atmosphere were explained. BLFO thin films obtained presents a rhombohedral structure. The BLFO films present dielectric and ferroelectric behaviors with dielectric permittivity and dielectric loss of approximately 81 and 0.0144 at 1 kHz. The Au/BLFO/Pt capacitor shows a hysteresis loop with remnant polarization of 20.6 mu C/cm(2) and coercive field of 53.88 kV/cm. The polarization switching and the fatigue behavior of the BLFO films were significantly enhanced.