Molecular Docking and Molecular Dynamic Studies of Semi-Synthetic Piperidine Alkaloids as Acetylcholinesterase Inhibitors

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

Peak Separation by Derivative Spectroscopy Applied to FTIR Analysis of Hydrolized Silica

Reliable spectral analysis is only achieved if the spectrum is thoroughly investigated in regard to all hidden and overlapped peaks. This paper describes the steps undertaken to find and separate such peaks in the range of 3000 to 4000 cm(-1) in the case of three different infrared absorption spectra of the glass surface of hydrolyzed silica optical fibers. Peak finding was done by the analysis of the second and fourth derivatives of the digital data, coupled with the available knowledge of infrared spectroscopy of silica-water interaction in the investigated range. Peak separation was accomplished by curve fitting with four different models. The model with the best fit was described by a sum of pure Gaussian peaks. Shoulder limit and detection limit maps were used to validate the revealed spectral features.

Alternative methodologies for the determination of aldehydes by capillary electrophoresis

This paper describes 2 alternative methodologies for the determination of selected aldehydes (formaldehyde, acetaldehyde, propionaldehyde, acrolein, and benzaldehyde) by capillary electrophoresis (CE), the first approach is based on the formation of aldehyde-bisulfite adducts and employs free solution CE with reversed electroosmotic flow and indirect detection, using 10 mmol/L 3,5-dinitrobenzoic acid (pH 4.5) containing 0.2 mmol/L cetyltrimethylammonium bromide as the electrolyte. This novel methodology showed a fairly good sensitivity to concentration, with detection limits with respect to a single aldehyde on the order of 10-40 mu g/L, a reasonable analysis time (separation was achieved in <8 min), and no need for sample manipulation. A second approach was proposed in which 2,4-dinitrophenylhydrazine derivatives of the aldehydes were detected in a micellar electrolyte medium (20 mmol/L berate buffer containing 50 mmol/L sodium dodecyl sulfate and 15 mmol/L beta-cyclodextrin). This latter methodology included a laborious sample preconcentration step and showed much poorer sensitivity (0.5-2 mg/L detection limit, with respect to a single aldehyde), despite the use of sodium chloride to promote sample stacking. Both methodologies proved adequate to evaluate aldehyde levels in vehicular emissions. Samples from the tailpipe exhaust of a passenger car vehicle without a catalytic converter and operated with an ethanol-based fuel were collected and analyzed; the results showed high levels of formaldehyde and acetaldehyde (0.41-6.1 ppm, v/v). The concentrations estimated by the 2 methodologies, which were not in good agreement, suggest the possibility of striking differences in sample collection efficiency, which was not the concern of this work.

Identification of polycyclic aromatic hydrocarbons and methoxylated phenols in wood smoke emitted during production of charcoal

More than 130 organic substances in dichloromethane-methanol (4: 1) extracts of particulate matter and the gaseous phase from wood burning for the production of charcoal have been identified by capillary gas chromatography coupled with low-resolution mass spectrometry (GC-MS), use of GC retention indices, and comparison with authentic standards. Many of the substances identified are methoxyphenols (derivatives of syringol and guaiacol), polycyclic aromatic hydrocarbons (PAH), oxidized PAH (oxy-PAH), and levoglucosan, the last being a monosoccharide derivative from the thermal breakdown of cellulose. The amount of unsubstituted PAH was greater than that of methyl- and dimethyl-substituted homologs.

Polycyclic aromatic hydrocarbons and other selected organic compounds in ambient air of Campo Grande City, Brazil

Fourteen samples of particulate matter and semi-volatile organic compounds were collected during 6 months in the city of Campo Grande, South Mato Grosso State, Brazil. Particle-bound polycyclic aromatic hydrocarbons (PAHs) were collected on Fluoropore PTFE filters and gas-phase PAHs were collected into sorbent tubes with XAD-2 resin. Both types of samples were extracted with a dichloromethane/methanol mixture (4:1 v/v), then the extracts were subjected to gas chromatography-mass spectrometry (GC-MS) analysis. PAHs, oxidized PAH (oxy-PAHs), phenols and methoxyphenols were identified by use of GC retention indices and MS files. The average value obtained for the sum of 15 PAHs was 21.05 ng m(-3) (range: 8.94-62.5 ng m(-3)). The presence of specific tracers and calculations of characteristic ratios (e.g. [Phe]/[Phe] + [Ant]) were used to identify the sources of the emissions of PAHs in the atmospheric samples. Levoglucosan (the anhydride of beta-glucose), retene (1-methyl-7-isopropylphenanthrene) and methoxyphenols (derivatives of syringol and guaiacol) and tracers for wood burning were identified. This study demonstrates that biomass burning from the rural zone is the main source of PAHs and emissions of other substances in the investigated site of Campo Grande. (c) 2004 Elsevier Ltd. All rights reserved.

Synthesis and in vitro evaluation of potential antichagasic dipeptide prodrugs of primaquine

American trypanosomiasis (Chagas' disease) is an endemic parasitic disease afflicting more than 20 million people in Latin America. Currently, therapy is unsatisfactory and only two drugs are available. Primaquine, an antimalarial drug, has trypanocidal activity. Dipeptide derivatives of primaquine, Phe-Arg-PQ, Lys-Arg-PQ, and Phe-Ala-PQ, were synthesized. The choice of the peptides was based on the primary specificity of cruzipain, the major cysteine proteinase from T. cruzi. The prodrugs obtained were tested on the LLC-MK2 cell culture infected with trypomastigotes forms of T. cruzi Phe-Arg-PQ, Lys-Arg-PQ, and Phe-Ala-PQ were active in all stages.

THE CATHODIC CLEAVAGE OF THE NITROBENZENESULFONYL GROUP FROM ALIPHATIC-AMINES IN N,N-DIMETHYLFORMAMIDE

The reduction of benzenesulfonyl derivatives of n-butylamine and N,N-di-n-butylamine with nitro substituents at the 2, 3 and 4 positions of the phenyl ring in N,N-dimethylformamide is reported. The N,N-di-n-butyl-4- and N-n-butyl-2-nitrobenzenesulfonamides are reduced in two cathodic steps. The first one, at about -0.90 V vs. SCE, a reversible one-electron process, gives a stable anion radical. The second reduction step at -1.70 V vs. SCE leads to cleavage of the S-N bond in good yields (> 70%). It is shown that the reduction of the N-n-butyl-3- and N-n-butyl-4-nitrobenzenesulfonamide is different, with three reduction steps. The first reduction step occurs with the formation of an unstable anion radical, which decomposes via N-H bond cleavage. The reduction of this sulfonamide anion occurs at -1.16 V vs. SCE and the third cathodic step arises at -1.70 V vs. SCE when the remaining radical anion is reduced to its dianion. The S-N bond cleavage is rapid but is always a minor process. The mechanisms of the reduction are discussed.

Composition for a class of generalized functions in Colombeau's theory

In Colombeau's theory, given an open subset Ω of ℝn, there is a differential algebra G(Ω) of generalized functions which contains in a natural way the space D′(Ω) of distributions as a vector subspace. There is also a simpler version of the algebra G,(Ω). Although this subalgebra does not contain, in canonical way, the space D′(Ω) is enough for most applications. This work is developed in the simplified generalized functions framework. In several applications it is necessary to compute higher intrinsic derivatives of generalized functions, and since these derivatives are multilinear maps, it is necessary to define the space of generalized functions in Banach spaces. In this article we introduce the composite function for a special class of generalized mappings (defined in open subsets of Banach spaces with values in Banach spaces) and we compute the higher intrinsic derivative of this composite function.

Improving the stability conditions of TS fuzzy systems with fuzzy Lyapunov functions

In this paper, the fuzzy Lyapunov function approach is considered for stabilizing continuous-time Takagi-Sugeno fuzzy systems. Previous linear matrix inequality (LMI) stability conditions are relaxed by exploring further the properties of the time derivatives of premise membership functions and by introducing a slack LMI variable into the problem formulation. The stability results are thus used in the state feedback design which is also solved in terms of LMIs. Numerical examples illustrate the efficiency of the new stabilizing conditions presented. © 2011 IFAC.

Spermatogenesis of Zaprionus indianus and Zaprionus sepsoides (Diptera, Drosophilidae): Cytochemical, structural and ultrastructural characterization

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Stability of nonlinear system using takagi-sugeno fuzzy models and hyper-rectangle of LMIs

This paper presents a theorem based on the hyper-rectangle defined by the closed set of the time derivatives of the membership functions of Takagi-Sugeno fuzzy systems. This result is also based on Linear Matrix Inequalities and allows the reduction of the conservatism of the stability analysis in the sense of Lyapunov. The theorem generalizes previous results available in the literature. © 2013 Brazilian Society for Automatics - SBA.

Characterization of flavonoids and phenolic acids in Myrcia bella cambess. Using FIA-ESI-IT-MSn and HPLC-PAD-ESI-IT-MS combined with NMR

The leaves of Myrcia DC. ex Guill species are used in traditional medicine and are also exploited commercially as herbal drugs for the treatment of diabetes mellitus. The present work aimed to assess the qualitative and quantitative profiles of M. bella hydroalcoholic extract, due to these uses, since the existing legislation in Brazil determines that a standard method must be developed in order to be used for quality control of raw plant materials. The current study identified eleven known flavonoid-O-glycosides and six acylated flavonoid derivatives of myricetin and quercetin, together with two kaempferol glycosides and phenolic acids such as caffeic acid, ethil galate, gallic acid and quinic acid. In total, 24 constituents were characterized, by means of extensive preparative chromatographic analyses, along with MS and NMR techniques. An HPLC-PAD-ESI-ITMS and FIA-ESI-IT-MSn method were developed for rapid identification of acylated flavonoids, flavonoid-O- glycosides derivatives of myricetin and quercetin and phenolic acids in the hydroalcoholic M. bella leaves extract. The FIA-ESI-IT-MS techinique is a powerful tool for direct and rapid identification of the constituents after isolation and NMR characterization. Thus, it could be used as an initial method for identification of authentic samples concerning quality control of Myrcia spp extracts. © 2013 by the authors.

Reducing the conservatism of LMI-based stabilisation conditions for TS fuzzy systems using fuzzy Lyapunov functions

In this article, the fuzzy Lyapunov function approach is considered for stabilising continuous-time Takagi-Sugeno fuzzy systems. Previous linear matrix inequality (LMI) stability conditions are relaxed by exploring further the properties of the time derivatives of premise membership functions and by introducing slack LMI variables into the problem formulation. The relaxation conditions given can also be used with a class of fuzzy Lyapunov functions which also depends on the membership function first-order time-derivative. The stability results are thus extended to systems with large number of rules under membership function order relations and used to design parallel-distributed compensation (PDC) fuzzy controllers which are also solved in terms of LMIs. Numerical examples illustrate the efficiency of the new stabilising conditions presented. © 2013 Copyright Taylor and Francis Group, LLC.

Chromatic characteristics and color-related phenolic composition of Brazilian young red wines made from the hybrid grape cultivar BRS Violeta (BRS Rúbea×IAC 1398-21)

The color characteristics and the phenolic composition related to color of young red wines elaborated with the hybrid grape cultivar BRS Violeta, developed for its adaptation to sub-tropical climates in Brazil, have been studied. These wines are characterized with a deep red-purplish color, reaching color intensity averaging 24 units. In spite of being young red wines elaborated with short maceration time, their content in total polyphenols was very high (around 3692. mg/L, as gallic acid equivalents), especially when compared to similar Vitis vinifera young red wines. Within polyphenols, anthocyanins predominated (around 2037. mg/L, as malvidin 3,5-diglucoside equivalents) and they were almost exclusively anthocyanidin 3,5-glucosides (ca. 97%), mainly built from B-ring tri-substituted anthocyanidins (delphinidin. >. petunidin. ≈. malvidin) and having high proportion of p-coumaroylated derivatives (ca. 28%) that confer higher stability. The content of hydroxycinnamic acid derivatives was also remarkable (ca. 95. mg/L, as caffeic acid equivalents) and unknown glucose derivatives of p-coumaric acid accounted for ca. 42% of total HCAD. Finally, these found flavonols were mainly based on myricetin whereas kaempferol derivatives were missing, their total content being within the ranges usually found for V. vinifera wines, but reaching their top values (ca. 91. mg/L, as quercetin 3-glucoside equivalents). All the aforementioned data suggest that Violeta wine could be considered an important dietary source of healthy polyphenols with a moderate alcoholic content (ca. 11.6%). © 2013 Elsevier Ltd.

Obtenção de derivados semissintéticos dos alcalóides (-) - cassina e (-) e espectalina e avaliação do potencial antimalárico

Pós-graduação em Química - IQ