Dádiva ou maldição de um bem mineral : o conflito entre o uso controlado e seguro do amianto e o seu banimento total

Consultoria Legislativa - Área XI - Meio Ambiente e Direito Ambiental, Organização Territorial e Desenvolvimento Urbano e Regional.

A definição do número total de representantes na Câmara dos Deputados em face da possível criação de novos Estados

Consultoria Legislativa - Área XIX - Ciência Política.

Systhema de medidas adoptaveis para a progressiva e total extincção do trafico, e da escravatura no Brasil

Proposta da Sociedade ao Governo Imperial para a gradual e total extinção da escravatura no Brasil.

Rapid determination of total CLA concentration in beef fat

[EN]Conjugated linoleic acid (CLA) has many potential healthful properties, and beef is naturally enriched with CLA. Simple and rapid methods to measure total CLA were investigated to enable sorting of beef carcasses with potential enhanced economic value. Direct alcohol extraction combined with measuring absorbance was simple, accurate and perhaps the most viable method for rapid carcass sorting compared to methods using saponification or methylation followed by extraction.

Institutional designs to face the dark side of total allowable catches

Setting total allowable catches (TACs) is an endogenous process in which different agents and institutions, often with conflicting interests and opportunistic behaviour, try to influence policy-makers. Such policy-makers, far from being the benevolent social planners many would wish them to be, may also pursue self-interest when making final decisions. Although restricted knowledge of stock abundance and population dynamics, and weakness in enforcement, have effects, these other factors may explain the reason why TAC management has failed to guarantee sustainable exploitation of fish resources. Rejecting the exogeneity of the TAC and taking advantage of fruitful debate on economic policy (i.e. the rules vs. discretion debate, and that surrounding the independence of central banks), two institutional developments are analysed as potential mechanisms to face up to misconceptions about TACs: long-term harvest control rules, and a central bank of fish.

Apoyo de la Contabilidad de Dirección Estratégica a la fidelización de la clientela a través de la motivación de los recursos humanos y de la gestión de la calidad total

El tema que vamos a desarrollar se orienta a la satisfacción y fidelización de la clientela como objetivo esencial de la empresa, lo que pemitirá aumentar la competitividad y pilotar la organización por la senda de la máxima eficiencia posible, en un enfoque sistématico de mejora continua hacia la excelencia empresarial.

Systhema de medidas adaptaveis para a progressiva e total extincção do trafico, e da escravatura no Brasil / confeccionado e aprovado pela Sociedade Contra o Trafico de Africanos, e Promotora da Colonisação, e da Civilisação dos Indigenas

Proposta da Sociedade ao Governo Imperial para a gradual e total extinção da escravatura no Brasil.

Geographical catch distribution of yellowfin and skipjack tuna in the Eastern Pacific Ocean, 1967-1970, and fleet and total catch statistics, 1962-1970

ENGLISH: Logbook records of tuna vessels fishing in the eastern Pacific Ocean were used to prepare charts showing the distribution of yellowfin tuna and skipjack catches by i-degree area, by quarter of the year, and by gear, for the years 1967-1970. Recent changes in the geographical distribution of yellowfin catch are illustrated. Also given are annual catch statistics and the composition of the international tuna fishing fleets which operated in the Commission's Yellowfin Regulatory Area each year, 1962-1970. SPANISH: Los registros de los cuadernos de bitácora de los barcos pesqueros de atún en el Océano Pacífico oriental se usaron para preparar gráficos que presentan para los años de 1967-1970, la distribución de captura del atún aleta amarilla y barrilete por área de 1 grado, trimestre del año y, por las artes. Se ilustran los recientes cambios en la distribución geográfica de la captura del atún aleta amarilla. Se presentan también las estadísticas de captura anual y la composición de la flota internacional de pesca, que explota cada año el Area Reglamentaria de la Comisión, 1962-1970. (PDF contains 95 pages.)

Geographical distribution of yellowfin and skipjack tuna catches in the Eastern Pacific Ocean, and fleet and total catch statistics, 1971-1974

ENGLISH: Logbook records of purse seiners and baitboats fishing for yellowfin and skipjack tunas in the eastern Pacific Ocean were used to prepare charts showing the distribution of catches by l-degree area and quarter of the year for each gear and regulation status, for the years 1971-1974. Changes in geographical distribution of the catch over the four-year period are discernible. Information on annual catch statistics and fleet composition by country is presented. SPANISH: Los registros de bitácora de los cerqueros y clíperes (barcos de carnada) que pescan atún aleta amarilla y barrilete en el Océano Pacífico oriental se emplearon para preparar los diagramas en los que se indica la distribución de las capturas por área de 1 grado y trimestre, correspondiente a cada arte y condición reglamentaria en los años de 1971 a 1974. Se pueden distinguir los cambios en la distribución geográfica de la captura durante el período de cuatro años. Se presenta la información por país sobre las estadísticas de la captura anual y la composicón de la flota. (PDF contains 116 pages.)

Geographical distribution of yellowfin and skipjack tuna catches in the Eastern Pacific Ocean, and fleet and total catch statistics, 1975-1978

ENGLISH: Logbook records of purse seiners and baitboats fishing for yellowfin and skipjack tunas in the eastern Pacific Ocean were used to prepare charts showing the distribution of catches by one-degree area and quarter of the year for each gear and regulation status, for the years 1975-1978. Changes in geographical distribution of the catch over the four-year period are described. Information on annual catch statistics and fleet composition by country is presented. SPANISH: Se emplearon los registros de bitácora de las embarcaciones cerqueras y de carnada que pescan atún aleta amarilla y barrilete en el Océano Pacífico oriental, para preparar los diagramas que indican la distribución de captura por zonas de un grado y trimestres del año de cada arte y condición de las reglamentaciones, en los años de 19'75 a 1978. Se describen los cambios de la distribución geográfica de la captura durante un período de cuatro Se presenta la información, por país, de las estadísticas de captura y de la composición de la flota. (PDF contains 120 pages.)

The intramolecular Buchner reaction of α-diazo-β-ketonitriles : development and application to the total synthesis of (+)-Salvileucalin B

Since its discovery in 1896, the Buchner reaction has fascinated chemists for more than a century. The highly reactive nature of the carbene intermediates allows for facile dearomatization of stable aromatic rings, and provides access to a diverse array of cyclopropane and seven-membered ring architectures. The power inherent in this transformation has been exploited in the context of a natural product total synthesis and methodology studies.

The total synthesis work details efforts employed in the enantioselective total synthesis of (+)-salvileucalin B. The fully-substituted cyclopropane within the core of the molecule arises from an unprecedented intramolecular Buchner reaction involving a highly functionalized arene and an α-diazo-β-ketonitrile. An unusual retro-Claisen rearrangement of a complex late-stage intermediate was discovered on route to the natural product.

The unique reactivity of α-diazo-β-ketonitriles toward arene cyclopropanation was then investigated in a broader methodological study. This specific di-substituted diazo moiety possesses hitherto unreported selectivity in intramolecular Buchner reactions. This technology was enables the preparation of highly functionalized norcaradienes and cyclopropanes, which themselves undergo various ring opening transformations to afford complex polycyclic structures.

Finally, an enantioselective variant of the intramolecular Buchner reaction is described. Various chiral copper and dirhodium catalysts afforded moderate stereoinduction in the cyclization event.

Palladium-catalyzed asymmetric allylic alkylation: insights, application toward cyclopentanoid and cycloheptanoid molecules, and the total synthesis of several daucane sesquiterpenes

The asymmetric construction of quaternary stereocenters is a topic of great interest in the organic chemistry community given their prevalence in natural products and biologically active molecules. Over the last decade, the Stoltz group has pursued the synthesis of this challenging motif via a palladium-catalyzed allylic alkylation using chiral phosphinooxazoline (PHOX) ligands. Recent results indicate that the alkylation of lactams and imides consistently proceeds with enantioselectivities substantially higher than any other substrate class previously examined in this system. This observation prompted exploration of the characteristics that distinguish these molecules as superior alkylation substrates, resulting in newfound insights and marked improvements in the allylic alkylation of carbocyclic compounds.

General routes to cyclopentanoid and cycloheptanoid core structures have been developed that incorporate the palladium-catalyzed allylic alkylation as a key transformation. The unique reactivity of α-quaternary vinylogous esters upon addition of hydride or organometallic reagents enables divergent access to γ-quaternary acylcyclopentenes or cycloheptenones through respective ring contraction or carbonyl transposition pathways. Derivatization of the resulting molecules provides a series of mono-, bi-, and tricyclic systems that can serve as valuable intermediates for the total synthesis of complex natural products.

The allylic alkylation and ring contraction methodology has been employed to prepare variably functionalized bicyclo[5.3.0]decane molecules and enables the enantioselective total syntheses of daucene, daucenal, epoxydaucenal B, and 14-p-anisoyloxydauc-4,8-diene. This route overcomes the challenge of accessing β-substituted acylcyclopentenes by employing a siloxyenone to effect the Grignard addition and ring opening in a single step. Subsequent ring-closing metathesis and aldol reactions form the hydroazulene core of these targets. Derivatization of a key enone intermediate allows access to either the daucane sesquiterpene or sphenobolane diterpene carbon skeletons, as well as other oxygenated scaffolds.

Progress towards the total synthesis of a spermine-conjugated dynemicin analog

Progress towards the synthesis of the spermine-conjugated Dynemicin analog 4 is described. The synthetic route starts with the Michael addition of menthyl acetoacetate to trans-ethyl crotonate followed by a Dieckman condensation to form the cyclohexanedione 14 which, through a series of chemical reactions, is transformed into the quinone imine 6. Key features in the route include the Suzuki coupling reaction of the aryl boronic acid 11 and the enol triflate 12, thermal deprotection/internal amidation of the biaryl 19, cis addition of the (Z)-enediyne 33 to the quinoline 25, intramolecular acetylide addition to a carbonyl within the ketone 29, and an addition/elimination of the cyanophthalide to the quinone imine 6 to form the anthraquinone 36 utilizing the Kraus and Sugimoto methodology.

New strategies for the total synthesis of aza-propellane natural products

The propellane alkaloids comprise a large class of natural products that possess varying degrees of structural complexity and biological activity. The earliest of these to be isolated was acutumine, a chlorinated alkaloid that has been shown to exhibit selective T-cell cytotoxicity and antiamnesic properties. Alternatively, the hasubanan family of natural products has garnered considerable attention from the synthetic community in part due to its structural similarities to morphine. While these alkaloids have been the subject of numerous synthetic studies over the last forty years, very few enantioselective total syntheses have been reported to date.

As part of a research program directed towards the synthesis of various alkaloid natural products, we have developed a unified strategy for the preparation of the hasubanan and acutumine alkaloids. Specifically, a highly diastereoselective 1,2-addition of organometallic reagents to benzoquinone-derived tert-butanesulfinimines was established, which provides access to enantioenriched 4-aminocyclohexadienone products. This methodology enabled the enantioselective construction of functionalized dihydroindolones, which were found to undergo intramolecular Friedel-Crafts conjugate additions to furnish the propellane cores of several hasubanan alkaloids. As a result of these studies, the first enantioselective total syntheses of 8-demethoxyrunanine and cepharatines A, C, and D were accomplished in 9-11 steps from commercially available starting materials.

More recent efforts have focused on applying the sulfinimine methodology to the synthesis of a more structurally complex propellane alkaloid, acutumine. Extensive studies have determined that a properly functionalized dihydroindolone undergoes a photochemical [2+2] cycloaddition followed by a lactone fragmentation/Dieckmann cyclization to establish the carbocyclic framework of the natural product. The preparation of more appropriately oxidized propellane intermediates is currently under investigation, and is anticipated to facilitate our synthetic endeavors toward acutumine.