Synthesis and characterization of mono- and bis-ligand zinc(II) and cadmium(II) complexes of the di-2-pyridylketone Schiff base of S-benzyl dithiocarbazate (Hdpksbz) and the X-ray crystal structures of the [Zn(dpksbz)2] and [Cd(dpksbz)NCS]2 complexes

New mono- and bis-chelated zinc(II) and cadmium(II) complexes of formula, [M(dpksbz)NCS] (dpksbz = anionic form of the di-2-pyridylketone Schiff base of S-benzyldithiocarbazate) and [M(dpksbz)(2)] (M = Zn-II, Cd-II) have been prepared and characterized. The structure of the bis-ligand complex, [Zn(dpksbZ)(2)] has been determined by X-ray diffraction. The complex has a distorted octahedral geometry in which the ligands are coordinated to the zinc(II) ion as uninegatively charged tridentate chelates via the thiolate sulfur atoms, the azomethine nitrogen atoms and the pyridine nitrogen atoms. The distortion from a regular octahedral geometry is attributed to the restricted bite angles of the Schiff base ligands. X-ray structural analysis shows that the [Cd(dpksbz)NCS](2) complex is a centrosymmetric dimer in which each of the cadmium(II) ions adopts a five-coordinate, approximately square-pyramidal configuration with the Schiff base acting as a tetradentate chelating agent coordinating a cadmium(II) ion via one of the pyridine nitrogen atoms, the azomethine nitrogen atom and the thiolate sulfur atom; the second pyridine nitrogen atom is coordinated to the other cadmium(II) ion of the dimer. The fifth coordination position around each cadmium(II) is occupied by an N-bonded thiocyanate ligand. (C) 2003 Elsevier Science Ltd. All rights reserved.

The peroxisome proliferator-activated receptor beta/delta agonist, GW501516, regulates the expression of genes involved in lipid catabolism and energy uncoupling in skeletal muscle cells

Lipid homeostasis is controlled by the peroxisome proliferator-activated receptors (PPARalpha, -beta/delta, and -gamma) that function as fatty acid-dependent DNA-binding proteins that regulate lipid metabolism. In vitro and in vivo genetic and pharmacological studies have demonstrated PPARalpha regulates lipid catabolism. In contrast, PPARgamma regulates the conflicting process of lipid storage. However, relatively little is known about PPARbeta/delta in the context of target tissues, target genes, lipid homeostasis, and functional overlap with PPARalpha and -gamma. PPARbeta/delta, a very low-density lipoprotein sensor, is abundantly expressed in skeletal muscle, a major mass peripheral tissue that accounts for approximately 40% of total body weight. Skeletal muscle is a metabolically active tissue, and a primary site of glucose metabolism, fatty acid oxidation, and cholesterol efflux. Consequently, it has a significant role in insulin sensitivity, the blood-lipid profile, and lipid homeostasis. Surprisingly, the role of PPARbeta/delta in skeletal muscle has not been investigated. We utilize selective PPARalpha, -beta/delta, -gamma, and liver X receptor agonists in skeletal muscle cells to understand the functional role of PPARbeta/delta, and the complementary and/or contrasting roles of PPARs in this major mass peripheral tissue. Activation of PPARbeta/delta by GW501516 in skeletal muscle cells induces the expression of genes involved in preferential lipid utilization, beta-oxidation, cholesterol efflux, and energy uncoupling. Furthermore, we show that treatment of muscle cells with GW501516 increases apolipoprotein-A1 specific efflux of intracellular cholesterol, thus identifying this tissue as an important target of PPARbeta/delta agonists. Interestingly, fenofibrate induces genes involved in fructose uptake, and glycogen formation. In contrast, rosiglitazone-mediated activation of PPARgamma induces gene expression associated with glucose uptake, fatty acid synthesis, and lipid storage. Furthermore, we show that the PPAR-dependent reporter in the muscle carnitine palmitoyltransferase-1 promoter is directly regulated by PPARbeta/delta, and not PPARalpha in skeletal muscle cells in a PPARgamma coactivator-1-dependent manner. This study demonstrates that PPARs have distinct roles in skeletal muscle cells with respect to the regulation of lipid, carbohydrate, and energy homeostasis. Moreover, we surmise that PPARgamma/delta agonists would increase fatty acid catabolism, cholesterol efflux, and energy expenditure in muscle, and speculate selective activators of PPARbeta/delta may have therapeutic utility in the treatment of hyperlipidemia, atherosclerosis, and obesity.

New structure formation on gamma-irradiation of poly(chlorotrifluoroethylene)

The radiation chemistry of PCTFE at different temperatures has been studied. The polymer was irradiated under vacuum to absorbed doses of up to 1500 kGy. Three irradiation temperatures were chosen. These included ambient temperature, a temperature well above the T, and a temperature above the crystalline melting temperature. These were 298, 423 and 493 K, respectively. The formation of new structures was identified by solid-state FTIR and F-19 NMR. No branching was observed below the melting temperature, but branches were observed above the melting temperature. G-values for chain-end formation were 1.5 and 2.4 at room temperature and 423 K, respectively and the G-value for the formation of double bonds was found to be < 0.1. For the irradiations at 493 K, the G-values for the formation of chain ends, double bonds and branching points were 3.6, 0.2 and 0.5, respectively. The presence of long-chain branches within the polymer structure could not be proven for radiolysis at 493 K, but scission predominates and network formation does not occur upon irradiation. DSC studies of the polymers irradiated at ambient temperature were consistent with chain scission leading to an increase in the percentage crystallinity, as observed for other fluoropolymers. (C) 2003 Elsevier Science Ltd. All rights reserved.

The preparation of zinc(II) and cadmium(II) complexes of the pentadentate N3S2 ligand formed from 2,6-diacetylpyridine and S-benzyldithiocarbazate (H2SNNNS) and the X-ray crystal structure of the novel dimeric [Zn2(SNNNS)2] complex

The pentadentate chelating agent, 2,6-diacetylpyridinebis(S-benzyldithiocarbazate) (H2SNNNS) reacts with zinc(II) and cadmium(II) ions forming stable complexes of empirical formula, [M(SNNNS)] (M=Zn2+, Cd2+; SNNNS2 =doubly deprotonated anionic form of the Schiff base). These complexes have been characterized by a variety of physico-chemical techniques. IR and H-1 NMR spectral evidence indicate that the Schiff base coordinates to the zinc(II) and cadmium(II) ions via the pyridine nitrogen atoms, the azomethine nitrogen atoms and the mercaptide sulfur atoms. The crystal and molecular structure of the zinc(II) complex has been determined by X-ray diffraction. The complex is a dimer in which the pyridine nitrogen atom,the azomethine nitrogen atom and the thiolate sulfur atom from one ligand coordinate to one of the zinc(II) ions whereas the azomethine and thiolate sulfur atoms from another ligand complete pentacoordination around the zinc(II) ion, the ligands being coordinated in their deprotonated forms. The coordination geometry about each zinc(II) can be considered as intermediate between a square-pyramid and trigonal-bipyramid. The cadmium(II) complex is also assigned with a dimeric structure. (C) 2003 Elsevier Ltd. All rights reserved.

Radical formation on gamma-radiolysis of poly [(methacrylic acid)-co-acrylonitri

The radicals formed on gamma-radiolysis of a series of copolymers of methacrylic acid and acrylonitrile have been investigated by ESR spectroscopy. This series of copolymers spanned the full composition range and the study was carried out at 77 K and ambient temperature. The radicals formed in the copolymers at 77 and 303 K were found to be similar to those found in the two homopolymers, but in the intermediate composition range the presence of acrylonitrile propagation radicals was also detected. These radicals were not observed to be formed in significant quantities on the radiolysis of polyacrylonitrile. They are believed to result from a scission of the main chain at methacrylic acid/acrylonitrile diad sequences following loss of the methacrylic acid carboxyl group. At 77 K, the copolymers with high methacrylic acid contents were found to be more sensitive to radical formation than the methacrylic acid homopolymer, but this enhanced sensitivity was not evident at ambient temperature, where the G-values for radical formation for the copolymers were slightly less than the values for the homopolymers. (C) 2003 Society of Chemical Industry.

The synthesis and X-ray crystal structure of 6-bromo-2,4,4-trimethyl-cyclohex-2-enone

Regiospecific bromination of 2,4,4-trimethyl-cyclohex-2-enone was achieved and the X-ray crystal structure of 6-bromo-2,4,4-trimethyl-cyclohex-2-enone is presented.

The synthesis and X-ray crystal structure of 9-carboxyhexahydro-7-methoxy-4a,7-ethano-benzopyran-5-en-1-one

9-Carboxyhexahydro-7-methoxy-4a,7-ethano-benzopyran-5-en-1-one (1) was prepared and examined by X-ray crystallography to probe its potential as a new peptide scaffold/template. The crystal structure of the anhydride precursor 7-(2-acetoxyethyl)-4-methoxy-3a,4,7,7a-tetrahydro-4,7-ethanoisobenzofuran-1,3-dione (6) is also reported.

Modified logit life table system: Principles, empirical validation, and application

Despite its widespread use, the Coale-Demeny model life table system does not capture the extensive variation in age-specific mortality patterns observed in contemporary populations, particularly those of the countries of Eastern Europe and populations affected by HIV/AIDS. Although relational mortality models, such as the Brass logit system, can identify these variations, these models show systematic bias in their predictive ability as mortality levels depart from the standard. We propose a modification of the two-parameter Brass relational model. The modified model incorporates two additional age-specific correction factors (gamma(x), and theta(x)) based on mortality levels among children and adults, relative to the standard. Tests of predictive validity show deviations in age-specific mortality rates predicted by the proposed system to be 30-50 per cent lower than those predicted by the Coale-Demeny system and 15-40 per cent lower than those predicted using the original Brass system. The modified logit system is a two-parameter system, parameterized using values of l(5) and l(60).

Dimensional X: a dificuldade na obten????o da informa????o em meio a problemas na gest??o de pessoas

Ant??nio foi convidado para assumir um cargo em que deveria gerenciar os sistemas de informa????o de um grande minist??rio. Com a miss??o inicial de fornecer uma informa????o sobre a for??a de trabalho, percebeu que havia problemas que iam muito al??m da simples utiliza????o desses sistemas, como a pol??tica de capacita????o de pessoal, a rotatividade de servidores, a falta de integra????o entre as ??reas e outros problemas na ??rea de gest??o de pessoas

Caf?? com debate: rela????es Brasil x China: neg??cios, mercados, oportunidades

Os slides apresentam informa????es sobre as mudan??as pol??ticas na China, sobre a distribui????o de seu PIB, sua produ????o industrial, as particularidades de suas institui????es e seu sistema de inova????es. Encontram-se tamb??m dados a respeito das trocas comerciais entre a Am??rica Latina e aquele pa??s

10?? Encontro Nacional das Escolas de Governo: prepara????o X ENEG

Este documento apresenta os resultados do " X Encontro Nacional de Escolas de Governo", promovido pela ENAP e realizado na sede da escola em Bras??lia, nos dias 12 e 13 de agosto de 2014.

Estudo de algumas propriedades mecânicas da madeira de um híbrido clonal de Eucalyptus urophylla X Eucalyptus grandis

A procura por madeiras oriundas de reflorestamentos destinadas à serraria é uma realidade já há muitos anos, principalmente aquelas das espécies do gênero Eucalyptus. Visando buscar novas informações importantes para esse mercado, este trabalho objetivou determinar algumas propriedades mecânicas da madeira de um híbrido clonal de Eucalyptus urophylla x Eucalyptus grandis de duas idades e provenientes de talhadia simples e de reforma. Os resultados indicaram que a madeira desse híbrido apresenta boas características tecnológicas, destacando-se a segunda tora (a partir de 3 m) com as melhores propriedades de flexão estática (Módulo de Elasticidade - MOE e Módulo de Ruptura - MOR) e Compressão Axial das fibras. As árvores de maior idade (166 meses) e que sofreram dois desbastes apresentaram as melhores propriedades de flexão estática e compressão axial.

Fatores prognósticos no tratamento do carcinoma epidermóide da laringe: cirurgia conservadora x radical

O tratamento do carcinoma da laringe tem como desafio a cura do paciente e a preservação do órgão. OBJETIVO: A avaliação dos subsítios na disseminação do carcinoma e a sua influência no tratamento cirúrgico da laringe, no controle local e na sobrevida. MATERIAL E MÉTODO: Cento e sessenta pacientes tratados na Escola Paulista de Medicina - Hospital São Paulo, no período de janeiro de 1998 a dezembro de 2004, foram compilados para análise da disseminação do carcinoma dos subsítios da laringe. Foram incluídos pacientes com seguimento mínimo de 2 anos, após diagnóstico e tratamento. A avaliação estatística foi: Teste X2, Teste de Fisher e a Curva de Kaplan-Meier. Forma de Estudo: Estudo de Coorte Histórica Longitudinal (Trabalho Clínico Retrospectivo). RESULTADOS: A comissura posterior e a infraglote, respectivamente, foram significantes para a laringectomia total: tumores glóticos AC: (p=0,03) AP: (p=0,0001); AC: (p=0,0007) AP: (p<0,0001). A infraglote foi significante nos tumores G+SG na AP: (p=0,04), e na taxa de óbitos AP: (p=0,03). CONCLUSÃO: A laringectomia total é o tratamento de eleição na presença de alto comprometimento da comissura posterior e da infraglote. Esta última pode comprometer a sobrevida, conforme a invasão local, mesmo na presença de margens cirúrgicas livres.