Synthesis, characterization, thermal behavior, and DFT calculation of solid 1,4-bis(3-carboxy-3-oxo-prop-1-enyl) benzene of some trivalent lanthanides

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

New reductive addition of hard nucleophiles to 6,7-bis(methylsulfanyl)-1,4-dihydro-1,4-methanonaphthalene-5,8-dione

A new reaction mode of 6,7-bis(methylsulfanyl)-1,4-dihydro-1,4-methanonaphthalene-5,8-dione 1 with the hard nucleophiles sodium benzene- or methane-sulfinate and cyanide, in DMSO, at room temperature, leads to the unexpected hydroquinonoid products 3a-c. All the data are in agreement with a mechanistic pathway involving the initial attack of the hard nucleophile onto the hard carbonyl group, followed by a symbiotic re-attack of the oxygen on the incoming group. In the case of soft nucleophiles, reaction on the olefinic carbon of the enedione system is preferential.

Efeito do 1,3/1,6 beta-glucano no sistema imune de cadelas submetidas a ovário-histerectomia

Pós-graduação em Medicina Veterinária - FCAV

Um mesmo professor da 1ª à 4ª série do ensino fundamental: uma chance para o sucesso

This article discuses the ramifications of the restructuring of educational institutions of the state basic education in the state of São Paulo in 1996. The changes promoted by the Education Department included the distinction between physical space including students from lower grades of elementary school students and the second cycle of this level of education. More that issues relating to changes in itself, is important here to check the influence that managers exercise, especially school principals in the perception of the community (parents, students etc.) relative to the changes implemented in the field of education. v

Positron scattering from the cyclic ethers oxirane, 1,4-dioxane, and tetrahydropyran

In this paper we report original measurements of total cross sections (TCSs) for positron scattering from the cyclic ethers oxirane (C2H4O), 1,4-dioxane (C4H8O2), and tetrahydropyran (C5H10O). The present experiments focus on the low energy range from similar to 0.2 to 50 eV, with an energy resolution smaller than 300 meV. This study concludes our systematic investigation into TCSs for a class of organic compounds that can be thought of as sub-units or moieties to the nucleotides in living matter, and which as a consequence have become topical for scientists seeking to simulate particle tracks in matter. Note that as TCSs specify the mean free path between collisions in such simulations, they have enjoyed something of a recent renaissance in interest because of that application. For oxirane, we also report original Schwinger multichannel elastic integral cross section (ICS) calculations at the static and static plus polarisation levels, and with and without Born-closure that attempts to account for the permanent dipole moment of C2H4O. Those elastic ICSs are computed for the energy range 0.5-10 eV. To the best of our knowledge, there are no other experimental results or theoretical calculations against which we can compare the present positron TCSs. However, electron TCSs for oxirane (also known as ethylene oxide) and tetrahydropyran do currently exist in the literature and a comparison to them for each species will be presented. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3696378]

DM-1, sodium 4-[5-(4-hydroxy-3-methoxyphenyl)-3-oxo-penta-1,4-dienyl]-2-methoxy-phenolate: a curcumin analog with a synergic effect in combination with paclitaxel in breast cancer treatment

This paper describes a new method for the preparation of sodium 4-[5-(4-hydroxy-3-methoxyphenyl)-3-oxo-penta-1,4-dienyl]-2-methoxy-phenolate, DM-1, and 3-oxo-penta-1,4-dienyl-bis (2-methoxy-phenolate), DM-2. The aim of this work was to evaluate the antitumor effects of DM-1 in adjuvant chemotherapy for breast cancer treatment. Mice bearing mammary adenocarcinomas (Ehrlich ascites tumors) were treated with paclitaxel alone, DM-1 alone, and paclitaxel + DM-1. Tumor samples were used to perform cytological analysis by the Papanicolaou method and apoptosis analysis by annexin V and phosphorylated caspase 3. The paclitaxel + DM-1 group had decreased tumor areas and tumor volumes, and the frequency of metastasis was significantly reduced. This caused a decrease in cachexia, which is usually caused by the tumor. Furthermore, treatment with paclitaxel + DM-1 and DM-1 alone increased the occurrence of apoptosis up to 40% in tumor cells, which is 35% more than in the group treated with paclitaxel alone. This cell death was mainly caused through phosphorylated caspase 3 (11% increase in paclitaxel + DM-1 compared to the paclitaxel group), as confirmed by reduced malignancy criteria in the ascitic fluid. DM-1 emerges as a potential treatment for breast cancer and may act as an adjuvant in chemotherapy, enhancing antitumor drug activity with reduced side effects.

Electrochromic Properties of a Metallo-supramolecular Polymer Derived from Tetra(2-pyridyl-1,4-pyrazine) Ligands Integrated in Thin Multilayer Films

The electrochromic behavior of iron complexes derived from tetra-2-pyridyl-1,4-pyrazine (TPPZ) and a hexacyanoferrate species in polyelectrolytic multilayer adsorbed films is described for the first time. This complex macromolecule was deposited onto indium-tin oxide (ITO) substrates via self-assembly, and the morphology of the modified electrodes was studied using atomic force microscopy (AFM), which indicated that the hybrid film containing the polyelectrolyte multilayer and the iron complex was highly homogeneous and was approximately 50 nm thick. The modified electrodes exhibited excellent electrochromic behavior with both intense and persistent coloration as well as a chromatic contrast of approximately 70%. In addition, this system achieved high electrochromic efficiency (over 70 cm(2) C-1 at 630 nm) and a response time that could be measured in milliseconds. The electrode was cycled more than 10(3) times, indicating excellent stability.

Stereoselective Bioreduction of 1-(4-Methoxyphenyl)ethanone by Whole Cells of Marine-Derived Fungi

Nine strains of marine-derived fungi (Aspergillus sydowii Ce15, A. sydowii Ce19, Aspergillus sclerotiorum CBMAI 849, Bionectria sp. Ce5, Beauveria felina CBMAI 738, Cladosporium cladosporioides CBMAI 857, Mucor racemosus CBMAI 847, Penicillium citrinum CBMAI 1186, and Penicillium miczynskii Gc5) were screened, catalyzing the asymmetric bioreduction of 1-(4-methoxyphenyl) ethanone 1 to its corresponding 1-(4-methoxyphenyl) ethanol 2. A. sydowii Ce15 and Bionectria sp. Ce5 produced the enantiopure (R)-alcohol 2 (>99% ee) in accordance with the anti-Prelog rule and, the fungi B. felina CBMAI 738 (>99% ee) and P. citrinum CBMAI 1186 (69% ee) in accordance with the Prelog rule. Stereoselective bioreduction by whole cells of marine-derived fungi described by us is important for the production of new reductases from marine-derived fungi.

One-Pot, Three-Step Reaction of 5-[(Trimethylsilyl)ethynyl]pyrrolidin-2-one with Azides Catalyzed by Cu-I: Synthesis of a Novel Class of 1,4-Disubstituted 1,2,3-Triazoles

A very fast, easy and efficient synthesis is described for a novel and biologically important class of 1,4-disubstituted-4-(5-pyrrolidin-2-one)-1,2,3-triazoles by an ultrasound-assisted one-pot, three-step click reaction sequence of 5-[(trimethylsilyl)ethynyl]pyrrolidin-2-one with organic azides mediated by catalytic Cu-I salts.

Aniline-1,4-benzoquinone as a model system for the characterization of products from aniline oligomerization in low acidic media

Increase in the pH medium of aniline polymerization is used for giving products of different morphologies, which are often wrongly attributed to PANI chains. Infrared and Raman spectroscopic data, supported by quantum chemical calculations, show that aniline-1,4-benzoquinone (AnBzq) is a model system for the characterization of the products of aniline oligomerization in low acidic media. The Raman spectra excited at different laser lines reveal the bichromophoric nature of AnBzq, whose absorption bands at 550 nm and 440 nm can be attributed to pi-pi* transitions of the delocalized benzoquinone and amino-phenyl moieties, respectively. (C) 2012 Elsevier B.V. All rights reserved.

Lasiodiplodan, an exocellular (1 -> 6)-beta-d-glucan from Lasiodiplodia theobromae MMPI: production on glucose, fermentation kinetics, rheology and anti-proliferative activity

Lasiodiplodan, an exopolysaccharide of the (1 -> 6)-beta-d-glucan type, is produced by Lasiodiplodia theobromae MMPI when grown under submerged culture on glucose. The objective of this study was to evaluate lasiodiplodan production by examining the effects of carbon (glucose, fructose, maltose, sucrose) and nitrogen sources (KNO3, (NH4)(2)SO4, urea, yeast extract, peptone), its production in shake flasks compared to a stirred-tank bioreactor, and to study the rheology of lasiodiplodan, and lasiodiplodan's anti-proliferative effect on breast cancer MCF-7 cells. Although glucose (2.05 +/- A 0.05 g L-1), maltose (2.08 +/- A 0.04 g L-1) and yeast extract (2.46 +/- A 0.06 g L-1) produced the highest amounts of lasiodiplodan, urea as N source resulted in more lasiodiplodan per unit biomass than yeast extract (0.74 +/- A 0.006 vs. 0.22 +/- A 0.008 g g(-1)). A comparison of the fermentative parameters of L. theobromae MMPI in shake flasks and a stirred-tank bioreactor at 120 h on glucose as carbon source showed maximum lasiodiplodan production in agitated flasks (7.01 +/- A 0.07 g L-1) with a specific yield of 0.25 +/- A 0.57 g g(-1) and a volumetric productivity of 0.06 +/- A 0.001 g L-1 h(-1). A factorial 2(2) statistical design developed to evaluate the effect of glucose concentration (20-60 g L-1) and impeller speed (100-200 rpm) on lasiodiplodan production in the bioreactor showed the highest production (6.32 g L-1) at 72 h. Lasiodiplodan presented pseudoplastic behaviour, and the apparent viscosity increased at 60A degrees C in the presence of CaCl2. Anti-proliferative activity of lasiodiplodan was demonstrated in MCF-7 cells, which was time- and dose-dependent with an IC50 of 100 mu g lasiodiplodan mL(-1).

OSCILLATORY DYNAMICS IN SYSTEMS CONTAINING BROMATE AND 1,4-CYCLOHEXANEDIONE IN ACIDIC MEDIA. I. THE EFFECT OF TEMPERATURE.

OSCILLATORY DYNAMICS IN SYSTEMS CONTAINING BROMATE AND 1,4-CYCLOHEXANEDIONE IN ACIDIC MEDIA. I. THE EFFECT OF TEMPERATURE. We present in this work the influence of temperature on the dynamics of homogeneous chemical systems containing bromate and 1,4-cyclohexanedione (1,4-CHD) in acidic media. In particular, the following systems were studied: bromate/1,4-CHD/acid, bromate/1,4-CHD/ferroin/acid and bromate/1,4-CHD/trisbipyridine ruthenium/acid. Investigations were carried out by means of an electrochemical probe, at five temperatures between 5 and 45 degrees C. Activation energies (E-a) were estimated in different ways for the pre-oscillatory and oscillatory regimes. In any case, the E-a was found to depend on the catalyst, composition and initial concentrations. In addition, it was observed that ferroin and trisbipyridine ruthenium act as catalysts only during the transition between the induction period and oscillatory regime.

Both alpha(1)- and beta(1)-adrenoceptors in the bed nucleus of the stria terminalis are involved in the expression of conditioned contextual fear

BACKGROUND AND PURPOSE The bed nucleus of the stria terminalis (BNST) is a limbic structure that is involved in the expression of conditioned contextual fear. Among the numerous neural inputs to the BNST, noradrenergic synaptic terminals are prominent and some evidence suggests an activation of this noradrenergic neurotransmission in the BNST during aversive situations. Here, we have investigated the involvement of the BNST noradrenergic system in the modulation of behavioural and autonomic responses induced by conditioned contextual fear in rats. EXPERIMENTAL APPROACH Male Wistar rats with cannulae bilaterally implanted into the BNST were submitted to a 10 min conditioning session (6 footshocks, 1.5 ma/ 3 s). Twenty-four hours later freezing and autonomic responses (mean arterial pressure, heart rate and cutaneous temperature) to the conditioning box were measured for 10 min. The adrenoceptor antagonists were administered 10 min before the re-exposure to the aversive context. KEY RESULTS L-propranolol, a non-selective beta-adrenoceptor antagonist, and phentolamine, a non-selective a-adrenoceptor antagonist, reduced both freezing and autonomic responses induced by aversive context. Similar results were observed with CGP20712, a selective beta 1-adrenoceptor antagonist, and WB4101, a selective a1-antagonist, but not with ICI118,551, a selective beta 2-adrenoceptor antagonist or RX821002, a selective a2-antagonist. CONCLUSIONS AND IMPLICATIONS These findings support the idea that noradrenergic neurotransmission in the BNST via a1- and beta 1-adrenoceptors is involved in the expression of conditioned contextual fear.

1,4-Diamino-2-butanone, a putrescine analogue, promotes redox imbalance in Trypanosoma cruzi and mammalian cells

The putrescine analogue 1,4-diamino-2-butanone (DAB) is highly toxic to various microorganisms, including Trypanosoma cruzi. Similar to other a-aminocarbonyl metabolites. DAB exhibits pro-oxidant properties. DAB undergoes metal-catalyzed oxidation yielding H2O2, NH4+ ion, and a highly toxic alpha-oxoaldehyde. In vitro. DAB decreases mammalian cell viability associated with changes in redox balance. Here, we aim to clarify the DAB pro-oxidant effects on trypomastigotes and on intracellular T. cruzi amastigotes. DAB (0.05-5 mM) exposure in trypomastigotes, the infective stage of T. cruzi, leads to a decline in parasite viability (IC50 c.a. 0.2 mM DAB; 4 h incubation), changes in morphology, thiol redox imbalance, and increased TcSOD activity. Medium supplementation with catalase (2.5 mu M) protects trypomastigotes against DAB toxicity, while host cell invasion by trypomastigotes is hampered by DAB. Additionally, intracellular amastigotes are susceptible to DAB toxicity. Furthermore, pre-treatment with 100-500 mu M buthionine sulfoximine (BSO) of LLC-MK2 potentiates DAB cytotoxicity, whereas 5 mM N-acetyl-cysteine (NAC) protects cells from oxidative stress. Together, these data support the hypothesis that redox imbalance contributes to DAB cytotoxicity in both T. cruzi and mammalian host cells. (C) 2012 Elsevier Inc. All rights reserved.

5-(1-(4-phenyl)-3-(4-nitrophenyl)triazene)-10,15,20-triphenylporphyrin: a new triazene-porphyrin dye and its spectroelectrochemical properties

The new triazene-porphyrin dye 5-(1-(4-phenyl)-3-(4-nitrophenyl)triazene)-10,15,20-triphenylporphyrin, encompassing a reactive protonated triazene moiety, was prepared starting from meso-tetraphenylporphyrin (H2TPP), first converting it to the 5-(4-nitrophenyl)-10,15,20-triphenylporphyrin, then reducing to the 5-(4-aminophenyl)-10,15,20-tri(phenyl) porphyrin intermediate, and reacting with the diazonium salt of 4-nitroaniline; and characterized by spectroscopic and electrochemical methods. The absorption spectrum of the neutral species resembled the sum of H2TPP and of 1,3-bis(4-nitrophenyl) triazene spectrum, but the deprotonated anionic species showed more delocalized frontier orbitals, behaving as a push-pull system exhibiting triazenide-to-porphyrin charge-transfer transitions.