Non-thiazolidinedione antihyperglycemic agents. Part 4: synthesis of ( )-, (R)-(+)- and (S)-(-)-enantiomers of 2-oxy-3-arylpropanoic acids

. Haigh, David; Birrell, Helen C.; Cantello, Barrie C. C.; Hindley, Richard M.; Ramaswamy, Anantha; Rami, Harshad K.; Stevens, Nicola C. Department of Medicinal Chemistry, SmithKline Beecham Pharmaceuticals, Essex, UK. Tetrahedron: Asymmetry (1999), 10(7), 1335-1351. Publisher: Elsevier Science Ltd., CODEN: TASYE3 ISSN: 0957-4166. Journal written in English. CAN 131:144536 AN 1999:369513 CAPLUS (Copyright (C) 2009 ACS on SciFinder (R)) Abstract The synthesis of a new series of potent 2-oxy-3-arylpropanoic acid antihyperglycemic agents in both racemic and non-racemic form is described. (the biol. activity of these compds. was not reported here). Resoln. of racemic acids is accomplished via amide formation with either (S)-2-phenylglycinol or (S)-4-benzyl-2-oxazolidinone as complementary resolving agents. The target compds. were ?-alkoxy-4-[2-[(2-benzoxazolyl)amino]ethoxy]benzenepropanoic acid derivs.

L'ensemble des EDO d'ordres 2 et 3 invariantes sous SL(2,R) et leur discrétisation préservant les symétries

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Comparison between blue and green stimulated luminescence of Al(2)O(3):C

This paper presents a systematic comparison of OSL signals from Al(2)O(3):C when stimulated with blue and green light. Al(2)O(3):C detectors were irradiated with various doses and submitted to various bleaching regimes using yellow, green and blue light. Most of the investigations were carried out using Luxel (TM)-type detectors used in the commercial Luxet (TM) and InLight (TM) dosimetry systems (Landauer Inc.). Al(2)O(3):C single crystals and Al(2)O(3):C powder were also used to complement the investigations. The results show that, although blue stimulation provides faster readout times (OSL curves that decayed faster) and higher initial OSL intensity than green stimulation, blue stimulation introduced complicating factors. These include incomplete bleaching of the dosimetric trap when the Al(2)O(3):C detectors are bleached with yellow or green light and the OSL is recorded with blue light stimulation, and an increased residual level due to stimulation of charge carriers from deep traps. The results warrant caution when using blue stimulation to measure the OSL signal from Al(2)O(3):C detectors, particularly if the doses involved are low and the detectors have been previously exposed to high doses. (C) 2010 Elsevier Ltd. All rights reserved.

Spectroscopic Investigation on the Formation of a Dinuclear Me(2)SO-Ru(2)-Mercaptopyridine Bridged Complex: [Ru(2)Cl(3)(mu-pyS)(mu-dmso)(dmso)(4)]center dot 2H(2)O

A dinuclear ruthenium(II) complex double-bridged by an N-aromatic ligand 2-mercaptopyridine (2-pyridinethiol or 2-pyridyl mercaptan) and a methyl sulfoxide (dmso) have been characterized by X-ray crystallography. The reported compound with formula [Ru(2)Cl(3) (mu-pyS)(mu-dmso)(dmso)(4)] center dot 2H(2)O, [C(15)H(36)Cl(3)NO(7)S(6)Ru(2)] (P2/c, a = 13.8175(2) angstrom, b = 10.5608(2) angstrom, c = 21.3544 (3) angstrom, beta = 106.090(1)degrees, V = 2,994.05(8) angstrom(3), Z = 4) represents a seven-membered ring system with both rutheniums in an octahedral geometry. All the hydrogen bonds (C-H-Cl) and the van der Waals contacts give rise to three-dimensional network in the structure and add stability to the dinuclear compound. To our knowledge, this is the first time that the formation of a dinuclear ruthenium(II) complex double-bridged by an N-aromatic ligand 2-mercaptopyridine and dmso have been reported. The study also provided valuable insight into bioinorganic chemistry as continuing efforts are being made to develop metal-based cancer chemotherapeutics. A major feature of this paper is the resolution of a double bridged ruthenium structure which contributes to a better understanding of ruthenium reactivity.

Structural role of fluoride in the ion-conducting glass system B(2)O(3)-PbO-LiF studied by single- and double-resonance NMR

The local structure of an ion-conducting glass with nominal composition 50B(2)O(3)-10PbO-40LiF has been investigated by complementary (7)Li, (11)B, (19)F, and (207)Pb single- and double-resonance experiments. The results give insight into the structural role of the lithium fluoride additive in borate glasses: (1) LiF is seen to actively participate in the network transformation process contributing to the conversion of three- into four-coordinate boron units, as shown by (11)B single-resonance as well as by (11)B{(19)F} and (19)F{(11)B} double-resonance experiments. (2) (19)F signal quantification experiments suggest substantial fluoride loss, presumably caused by formation of volatile BF(3). A part of the fluoride remains in the dopant role, possibly in the form of small LiF-like cluster domains, which serve as a mobile ion supply. (3) The extent of lithium-fluorine and lead-fluorine interactions has been characterized by (7)Li{(19)F} and (207)Pb{(19)F} REDOR and SEDOR experiments. On the basis of these results, a quantitative structural description of this system has been developed.

On the use of 2,1,3-benzothiadiazole derivatives as selective live cell fluorescence imaging probes

Newly designed 2,1,3-benzothiadiazole-containing fluorescent probes with four excited state intramolecular proton transfer (ESIPT) sites were successfully tested in live cell-imaging assays using a confluent monolayer of human stem-cells (tissue). All tested dyes were compared with the commercially available DAPI and gave far better results. (c) 2010 Elsevier Ltd. All rights reserved.

Thermoluminescence and synchrotron radiation studies on the persistent luminescence of BaAl(2)O(4)/Eu(2+),Dy(3+)

The persistent luminescence materials, barium aluminates doped with Eu(2+) and Dy(3+) (BaAl(2)O(4): Eu(2+),Dy(3+)), were prepared with the combustion synthesis at temperatures between 400 and 600 degrees C as well as with the solid state reaction at 1500 degrees C. The concentrations of Eu(2+)/Dy(3+) (in mol% of the Ba amount) ranged from 0.1/0.1 to 1.0/3.0. The electronic and defect energy level structures were studied with thermoluminescence (TL) and synchrotron radiation (SR) spectroscopies: UV-VUV excitation and emission, as well as with X-ray absorption near-edge structure (XANES) methods. Theoretical calculations using the density functional theory (DFT) were carried out in order to compare with the experimental data. (C) 2010 Elsevier Inc. All rights reserved.

Persistent luminescence of Eu(2+) and Dy(3+) doped barium aluminate (BaAl(2)O(4):Eu(2+),Dy(3+)) materials

Polycrystalline Eu(2+) and Dy(3+) doped barium aluminate materials, BaAl(2)O(4):Eu(2+),Dy(3+), were prepared with solid state reactions at temperatures between 700 and 1500 degrees C. The influence of the thermal treatments on the stability, homogeneity and structure as well as to the UV-excited and persistent luminescence of the materials was investigated by X-ray powder diffraction, SEM imaging and infrared spectroscopies as well as by steady state luminescence spectroscopy and persistent luminescence decay curves, respectively. The IR spectra of the materials prepared at 250, 700, and 1500 degrees C follow the formation of BaAl(2)O(4) composition whereas the X-ray powder diffraction of compounds revealed how the hexagonal structure was obtained. The morphology of the materials at high temperatures indicated important aggregation due to sintering. The luminescence decay of the quite narrow Eu(2+) band at ca. 500 nm shows the presence of persistent luminescence after UV irradiation. The dopant (Eu(2+)) and co-clopant (Dy(3+)) concentrations affect the crystallinity and luminescence properties of the materials. (C) 2009 Elsevier B.V. All rights reserved.

Biolabeling with nanoparticles based on Y(2)O(3):Nd(3+) and luminescence detection in the near-infrared

Neodymium based fluorescence presents several advantages in comparison to conventional rare earth or enzyme-substrate based fluorescence emitting sources (e.g.Tb, HRP). Based on this fact we have herein explored a Nd-based fluoroimmunoassay. We efficiently detected the presence of an oxidized low-density lipoprotein (oxLDL) in human plasma a well-known marker for cardiovascular diseases, which causes around 30% of deaths worldwide. Conventional fluoroimmunoassay uses time-resolved luminescence techniques, with detection in the visible range, to eliminate the fluorescence background from the biological specimens. By using an immunoassay based on functionalized Y(2)O(3):Nd(3+) nanoparticles, where the excitation and emission processes in the Nd(3+) ion occur in the near-infrared (NIR) region, we have succeeded in eliminating the interferences from the biological fluorescence background, avoiding the use of time-resolved techniques. This yields higher emission intensity from the Nd(3+)-nanolabels and efficient detection of anti-oxidized low-density lipoproteins (anti-oxLDL) by Y(2)O(3):Nd(3+)-antibody-antigen conjugation, leading to a novel biolabeling method. (C) 2010 Elsevier B.V. All rights reserved.

Production of hydrogen via steam reforming of biofuels on Ni/CeO(2)-Al(2)O(3) catalysts promoted by noble metals

The catalytic activity of Ni/CeO(2)-Al(2)O(3) catalysts modified with noble metals (Pt, Ir, Pd and Ru) was investigated for the steam reform of ethanol and glycerol. The catalysts were characterized by the following techniques: Energy-dispersive X-ray, BET, X-ray diffraction, temperature-programmed reduction, UV-vis diffuse reflectance spectroscopy and X-ray absorption near edge structure (XANES). The results showed that the formation of inactive nickel aluminate was prevented by the presence of CeO(2) dispersed on alumina. The promoting effect of noble metals included a decrease in the reduction temperatures of NiO species interacting with the support, due to the hydrogen spillover effect. It was seen that the addition of noble metal stabilized the Ni sites in the reduced state along the reforming reaction, increasing the ethanol and glycerol conversions and decreasing the coke formation. The higher catalytic performance for the ethanol steam reforming at 600 degrees C and glycerol steam reforming was obtained for the NiPd and NiPt catalysts, respectively, which presented an effluent gaseous mixture with the highest H(2) yield with reasonably low amounts of CO. (c) 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Synthesis, spectral studies and X-ray crystal structure of N,N `-(+/-)-trans-1,2-cyclohexylenebis(3-ethoxysalicylideneamine) H-2(t-3-EtOsalchxn)

The synthesis, spectra and X-ray crystal structure of N,N`-(+/-)-trans-1,2-cyclohexylenebis(3-ethoxysalicylideneamine) H-2(t-3-EtOsalchxn), a salen-type ligand, are reported. The Schiff base was characterized by elemental analysis, m.p., IR, electronic spectra, H-1 and C-13 NMR spectra. The spectra are discussed and compared with those of N,N`-(+/-)-trans-1,2-cyclohexylenebis(salicylideneamine), H-2(t-salchxn). The electronic and IR spectra were also resolved by deconvolution. The influence of the ethoxy group on the IR, electronic spectrum, H-1 and C-13 NMR spectra is discussed. Strong intramolecular forces are present as supported by the IR and H-1 NMR spectra and the X-ray crystal structure. An intermolecular hydrogen bond is observed and appears twice in a pair of molecules in the unit cell. (c) 2007 Elsevier B.V. All rights reserved.

Synthesis, Characterization, and Electrocatalytic Activity toward Methanol Oxidation of Carbon-Supported Pt(x)-(RuO(2)-M)(1-x) Composite Ternary Catalysts (M = CeO(2), MoO(3), or PbO(x))

Carbon-supported platinum is commonly used as an anode electrocatalyst in low-temperature fuel cells fueled with methanol. The cost of Pt and the limited world supply are significant barriers for the widespread use of this type of fuel cell. Moreover, Pt used as anode material is readily poisoned by carbon monoxide produced as a byproduct of the alcohol oxidation. Although improvements in the catalytic performance for methanol oxidation were attained using Pt-Ru alloys, the state-of-the-art Pt-Ru catalyst needs further improvement because of relatively low catalytic activity and the high cost of noble Pt and Ru. For these reasons, the development of highly efficient ternary platinum-based catalysts is an important challenge. Thus, various compositions of ternary Pt(x)-(RuO(2)-M)(1-x)/C composites (M = CeO(2), MoO(3), or PbO(x)) were developed and further investigated as catalysts for the methanol electro-oxidation reaction. The characterization carried out by X-ray diffraction, energy-dispersive X-ray analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, and cyclic voltammetry point out that the different metallic oxides were successfully deposited on the Pt/C, producing small and well-controlled nanoparticles in the range of 2.8-4.2 nm. Electrochemical experiments demonstrated that the Pt(0.50)(RuO(2)-CeO(2))(0.50)/C composite displays the higher catalytic activity toward the methanol oxidation reaction (lowest onset potential of 207 mV and current densities taken at 450 mV, which are 140 times higher than those at commercial Pt/C), followed by the Pt(0.75)(RuO(2)-MoO(3))(0.25)/C composite. In addition, both of these composites produced low quantities of formic acid and formaldehyde when compared to a commercially available Pt(0.75)-Ru(0.25)/C composite (from E-Tek, Inc.), suggesting that the oxidation of methanol occurs mainly by a pathway that produces CO(2) forming the intermediary CO(ads).

Relatório de estágio do mestrado em ensino da educação física: Escola Básica dos 2º e 3º Ciclos de São Roque

O estágio pedagógico, teve como pano de fundo as linhas orientadoras do estágio, o qual foi exercido na Escola Básica dos 2º e 3º Ciclos de São Roque, nomeadamente, no 3º Ciclo no 9º ano de escolaridade. Este permitiu vivenciar e exercer um papel de professor, facultando conhecimentos e dificuldades associados ao primeiro contacto com a profissão de docente. As escolhas e decisões utilizadas ao longo do estágio, quer na prática lectiva, quer nas actividades desenvolvidas, foram fruto de um levantamento efectuado, de forma a dar resposta aos interesses identificados, designadamente, no âmbito das matérias alternativas, na rentabilização dos espaços e materiais que a escola proporciona e com vista a cumprir com o Projecto Curricular de Escola e com o Projecto Educativo. Com este relatório, procuramos entender o sentido de uma pedagogia da Educação Física, de uma unidade de ensino, bem como as suas matérias, o processo da avaliação adoptado, as estratégias aplicadas, os diversos tipos de recursos utilizados, como também todo o planeamento efectuado previamente, de forma a conduzir toda a nossa intervenção. Proporcionamos uma educação, como um processo que aponta garantir o desenvolvimento do indivíduo, nas suas competências e potencialidades, no âmbito da disciplina de Educação Física. Na análise que realizamos, averiguamos que grande parte das escolhas e decisões foram cumpridas pelos alunos e por nós, enquanto professoras estagiárias e daí surgiu a necessidade de descrever e de relatar todos os passos dados no estágio. Assim, possibilitamos aos alunos, um sentido de autonomia, de responsabilidade, de cooperação, de compreensão dos conteúdos e de certa forma, concedendo-lhes um papel de co-gestores, no sentido dos próprios gerirem os seus conhecimentos e competências. Assim, apresentamos uma realidade que está inserida num contexto particular, no qual adoptamos uma actuação coerente e integrada no processo pedagógico, no âmbito da docência da disciplina de Educação Física, que poderia ser diferente numa outra realidade escolar.

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)