Synthesis, Structure, and Phosphatase-Like Activity of a New Trinuclear Gd Complex with the Unsymmetrical Ligand H(3)L As a Model for Nucleases

The new trinuclear gadolinium complex [Gd(3)L(2)(NO(3))(2)(H(2)O)(4)]NO(3)center dot 8H(2)O (1) with the unsymmetrical ligand 2-[N-bis-(2-pyridylmethyl)aminomethyl]-4-methyl-6-[N-bis(2-hydroxy-2-oxoethyl)aminomethyl] phenol (H(3)L) was synthesized and characterized. The new ligand H(3)L was obtained in good yield. Complex I crystallizes in an orthorhombic cell, space group Pcab. Kinetic studies show that complex 1 is highly active in the hydrolysis of the substrate 2,4-bis(dinitrophenyl)phosphate (K(m) = 4.09 mM, V(max) = 2.68 x 10(-2) mM s(-1), and k(cat) = V(max)/[1] = 0.67 s(-1)). Through a potentiometric study and determination of the kinetic behavior of 1 in acetonitrile/water solution, the species present in solution could be identified, and a trinuclear monohydroxo species appears to be the most prominent catalyst under mild conditions. Complex 1 displays high efficiency in DNA hydrolytic cleavage, and complete kinetic studies were carried out (K(m) = 4.57 x 10(-4) M, K(cat)` = 3.42 h(-1), and k(cat)`/K(m) = 7.48 x 10(3) M(-1) h(-1)). Studies with a radical scavenger (dimethyl sulfoxide, DMSO) showed that it did not inhibit the activity, indicating the hydrolytic action of 1 in the cleavage of DNA, and studies on the incubation of distamycin with plasmid DNA suggest that 1 is regio-specific, interacting with the minor groove of DNA.

The Itajai foreland basin: a tectono-sedimentary record of the Ediacaran period, Southern Brazil

The Itajai Basin located in the southern border of the Luis Alves Microplate is considered as a peripheral foreland basin related to the Dom Feliciano Belt. It presents an excellent record of the Ediacaran period, and its upper parts display the best Brazilian example of Precambrian turbiditic deposits. The basal succession of Itajai Group is represented by sandstones and conglomerates (BaA(0) Formation) deposited in alluvial and deltaic-fan systems. The marine upper sequences correspond to the Ribeiro Carvalho (channelized and non-channelized proximal silty-argillaceous rhythmic turbidites), Ribeiro Neisse (arkosic sandstones and siltites), and Ribeiro do Bode (distal silty turbidites) formations. The ApiA(0)na Formation felsic volcanic rocks crosscut the sedimentary succession. The Cambrian Subida leucosyenogranite represents the last felsic magmatic activity to affect the Itajai Basin. The Brusque Group and the Florianpolis Batholith are proposed as source areas for the sediments of the upper sequence. For the lower continental units the source areas are the Santa Catarina, So Miguel and CamboriA(0) complexes. The lack of any oceanic crust in the Itajai Basin suggests that the marine units were deposited in a restricted, internal sea. The sedimentation started around 600 Ma and ended before 560 Ma as indicated by the emplacement of rhyolitic domes. The Itajai Basin is temporally and tectonically correlated with the Camaqu Basin in Rio Grande do Sul and the Arroyo del Soldado/Piriapolis Basin in Uruguay. It also has several tectono-sedimentary characteristics in common with the African-equivalent Nama Basin.

Deformation and geochronology of syntectonic granitoids emplaced in the Major Gercino Shear Zone, southeastern South America

The Major Gercino Shear Zone is one of the NE-SW lineaments that separate the Neoproterozoic Dom Feliciano Belt, of Brazil and Uruguay, into two different domains: a northwestern supracrustal domain from a southeastern granitoid domain. The shear zone, striking NE, is composed of protomylonites to ultramylonites with mainly dextral kinematic indicators. In Santa Catarina State, southern Brazil, the shear zone is composed of two mylonite belts. The mylonites have mineral orientations produced under greenschist fades conditions at a high strain rate. Strong flattening and coaxial deformation indicate the transpressive character, while the role of pure shear is emphasized by the orientation of the mylonite belts in relation to the inferred stress field component. The quartz microstructures point out that different dynamic recrystallization regimes and crystal plasticity were the dominant mechanisms of deformation during the mylonitization process. Additionally, the fabrics suggest that the glide systems are activated for deformation conditions compatible with the metamorphism in the middle greenschist facies. Elongated granitoid intrusions belonging to two petrographically, geochemically and isotopically distinct rock associations occur between the two mylonite belts. The structures observed in the granites result from a deformation range from magmatic to solid-state conditions points to a continuum of magma straining during and just after its crystallization. Conventional U-Pb analysis of multi-crystal zircon fractions yielded essentially identical ages of 609 +/- 16 Ma and 614 +/- 2 Ma for the two granitic associations, and constrain the transpressive phase of the shear zone. K-Ar ages of biotites between 585 and 560 Ma record the slow cooling and uplift of the intrusions. Some K-Ar ages of micas in regional mylonites are similar, suggesting that thermo-tectonic activity was intense up to this time, probably related to the agglutination of the granite belt to the supracrustal belt NW of the MGSZ. (C) 2009 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

The development of blowouts and foredunes in the Ilha Comprida barrier (Southeastern Brazil): the influence of Late Holocene climate changes on coastal sedimentation

Middle to Late Holocene barriers are conspicuous landforms in southeastern and southern Brazilian regions. The barriers in the coastal zones of northern Santa Catarina, Parana and Sao Paulo states (27 degrees 19`-24 degrees 00`S) are formed mainly by beach ridge alignments and many barriers present foredune and blowout alignments in their seaward portion. The development of these eolian landforms appears to record a regional shift in coastal dynamics and barrier building. In this context, the Ilha Comprida barrier stands out for its well-developed and well-preserved foredunes and blowouts. Based on the presence or not and type of eolian landforms, the Ilha Comprida barrier can be divided seaward into inner, middle and outer units. The inner unit is formed entirely by beach ridges. The middle unit comprises a narrow belt of blowouts (up to 15 m high) aligned alongshore. Blowout lobes pointing NNW are indicative of their generation by southern winds. The outer unit is represented by low (<= 1 m high) active or stabilized foredunes and a small transgressive dunefield (similar to 1 km(2)). Twenty-seven luminescence ages (SAR protocol) obtained for the beach ridges, foredunes, and blowouts of these three units allow definition of a precise chronology of these landforms and calculation of rates of coastal progradation. The inner unit presents ages greater than 1004 +/- 88 years. The blowouts of the middle unit show ages from 575 +/- 47 to 172 +/- 18 years. The ages of the outer unit are less than 108 +/- 10 years. Rates of coastal progradation for the inner and outer units are 0.71-0.82 m/year and 0.86-2.23 m/year, respectively. The main phase of blowout development correlates well with the Little Ice Age (LIA) climatic event. These results indicate that southern winds in subtropical Brazil became increasingly more intense and/or frequent during the LIA. These conditions persist to the present and are responsible for the development of the eolian landforms in the outer unit. Thus, barrier geomorphology can record global climatic events. The sensitivity of barrier systems in subtropical Brazil to Late Holocene climate changes was favored by the relative sea level stillstand during this time. Luminescence dating makes it possible to analyze barrier geomorphology during Late Holocene climate changes operating on timescales of a hundred to thousand years. These results improve our knowledge of barrier building and will help in the evaluation of the impact of future climate changes on coastal settings. (C) 2008 Elsevier Ltd. All rights reserved.

Grain size and heavy minerals of the Late Quaternary eolian sediments from the Imbituba-Jaguaruna coast, Southern Brazil: Depositional controls linked to relative sea-level changes

The stratigraphic subdivision and correlation of dune deposits is difficult, especially when age datings are not available. A better understanding of the controls on texture and composition of eolian sands is necessary to interpret ancient eolian sediments. The Imbituba-Jaguaruna coastal zone (Southern Brazil, 28 degrees-29 degrees S) stands out due to its four well-preserved Late Pleistocene (eolian generation 1) to Holocene eolian units (eolian generations 2, 3, and 4). In this study, we evaluate the grain-size and heavy-mineral characteristics of the Imbituba-Jaguartma eolian units through statistical analysis of hundreds of sediment samples. Grain-size parameters and heavy-mineral content allow us to distinguish the Pleistocene from the Holocene units. The grain size displays a pattern of fining and better sorting from generation 1 (older) to 4 (younger), whereas the content of mechanically stable (dense and hard) heavy minerals decreases from eolian generation 1 to 4. The variation in grain size and heavy-mineral content records shifts in the origin and balance (input versus output) of eolian sediment supply attributable mainly to relative sea-level changes. Dunefields submitted to relative sea-level lowstand conditions (eolian generation 1) are characterized by lower accumulation rates and intense post-depositional dissection by fluvial incision. Low accumulation rates favor deflation in the eolian system, which promotes concentration of denser and stable heavy minerals (increase of ZTR index) as well as coarsening of eolian sands. Dissection involves the selective removal of finer sediments and less dense heavy minerals to the coastal source area. Under a high rate of relative sea-level rise and transgression (eolian generation 2), coastal erosion prevents deflation through high input of sediments to the coastal eolian source. This condition favors dunefield growth. Coastal erosion feeds sand from local sources to the eolian system. including sands from previous dunefields (eolian generation 1) and from drowned incised valleys. Therefore, dunefields corresponding to transgressive phases inherit the grain-size and heavy-mineral characteristics of previous dunefields, leading to selective enrichment of finer sands and lighter minerals. Eolian generations 3 and 4 developed during a regressive-progradational phase (Holocene relative sea level highstand). The high rate of sediment supply during the highstand phase prevents deflation. The lack of coastal erosion favors sediment supply from distal sources (fluvial sediments rich in unstable heavy minerals). Thus, dunefields of transgressive and highstand systems tracts may be distinguished from dunefields of the lowstand systems tract through high rates of accumulation (low deflation) in the former. The sediment source of the transgressive dunefields (high input of previously deposited coastal sands) differs from that of the highstand dunefields (high input of fluvial distal sands). Based on this case study, we propose a general framework for the relation between relative sea level, sediment supply and the texture and mineralogy of eolian sediments deposited in siliciclastic wet coastal zones similar to the Imbituba-Jaguaruna coast (C) 2009 Elsevier B.V. All rights reserved.

POSTMARITAL RESIDENCE PRACTICE IN SOUTHERN BRAZILIAN COASTAL GROUPS: CONTINUITY AND CHANGE

The coastal plains of the States of Parana and Santa Catarina, in Southern Brazil, were first settled around 6000 B.P. by shellmound builders, a successful fisher-hunter-gatherer population that inhabited the coastal lowlands practically unchanged for almost five thousand years. Shellmounds were typically occupied as residential sites as well as cemeteries, and are usually associated with rich alimentary zones. Around 1200 B.P., the first evidence of ceramics brought from the interior is found in coastal areas, and together with ceramics there is a progressive abandonment of shellmound construction in favor of flat cold shallow sites. Here we consider if these changes were reflected in the postmarital residence practice of coastal groups, i.e., if the arrival or intensification of contact with groups from the interior resulted in changes in this aspect of social structure among the coastal groups. To test the postmarital residence practice we analyzed within-group variability ratios between males and females, following previous studies on the topic. and between-group, correlations between Mahalanobis distances and geographic distances. The results suggest that in the pre-ceramic series a matrilocal, postmarital residential system predominated, while in the ceramic period there was a shift toward patrilocality. This favors the hypothesis that the changes experienced by coastal groups after 1200 B.P. affected not only their economy and material culture, but important aspects of their sociopolitical organization as well.

In vitro morphogenesis and cell suspension culture establishment in Piper solmsianum C. DC. (Piperaceae)

In vitro morphogenesis and cell suspension culture establishment in Piper solmsianum C. DC. (Piperaceae)). Piper solmsianum is a shrub from Southeast Brazil in which many biologically active compounds were identified. The aim of this work was to establish a cell suspension culture system for this species. With this in mind, petiole and leaf explants obtained from in vitro plantlets were cultured in the presence of different plant growth regulator combinations (IAA, NAA, 2,4-D and BA). Root and indirect shoot adventitious formation, detected by histological analysis, was observed. Besides the different combinations of plant growth regulators, light regime and the supplement of activated charcoal (1.5 mg.l(-1)) were tested for callus induction and growth. Cultures maintained in light, on a 0.2 mg.l(-1) 2,4-D and 2 mg.l(-1) BA supplemented medium, and in the absence of activated charcoal, showed the highest calli fresh matter increment. From a callus culture, cell suspension cultures were established and their growth and metabolite accumulation studied. The achieved results may be useful for further characterization of the activated secondary metabolites pathways in in vitro systems of P. solmsianum.

Development of a fast capillary electrophoresis method to determine inorganic cations in biodiesel samples

The aim of this study was to develop a fast capillary electrophoresis method for the determination of inorganic cations (Na(+), K(+), Ca(2+), Mg(2+)) in biodiesel samples, using barium (Ba(2+)) as the internal standard. The running electrolyte was optimized through effective mobility curves in order to select the co-ion and Peakmaster software was used to determine electromigration dispersion and buffer capacity. The optimum background electrolyte was composed of 10 mmol L(-1) imidazole and 40 mmol L(-1) of acetic acid. Separation was conducted in a fused-silica capillary (32 cm total length and 23.5 cm effective length, 50 mu m I.D.), with indirect UV detection at 214 nm. The migration time was only 36 s. In order to obtain the optimized conditions for extraction, a fractional factorial experimental design was used. The variables investigated were biodiesel mass, pH, extractant volume, agitation and sonication time. The optimum conditions were: biodiesel mass of 200 mg, extractant volume of 200 mu L. and agitation of 20 min. The method is characterized by good linearity in the concentration range of 0.5-20 mg kg(-1) (r > 0.999), limit of detection was equal to 0.3 mg kg(-1), inter-day precision was equal to 1.88% and recovery in the range of 88.0-120%. The developed method was successfully applied to the determination of cations in biodiesel samples. (c) 2010 Elsevier B.V. All rights reserved.

Development of a fast capillary electrophoresis method for the determination of propranolol-Total analysis time reduction strategies

The aim of this study was to develop a fast capillary electrophoresis method for the determination of propranolol in pharmaceutical preparations. In the method development the pH and constituents of the background electrolyte were selected using the effective mobility versus pH curves. Benzylamine was used as the internal standard. The background electrolyte was composed of 60 mmol L(-1) tris(hydroxymethyl)aminomethane and 30 mmol L(-1) 2-hydroxyisobutyric acid,at pH 8.1. Separation was conducted in a fused-silica capillary (32 cm total length and 8.5 cm effective length, 50 mu m I.D.) with a short-end injection configuration and direct UV detection at 214 nm. The run time was only 14 s. Three different strategies were studied in order to develop a fast CE method with low total analysis time for propranolol analysis: low flush time (Lflush) 35 runs/h, without flush (Wflush) 52 runs/h, and Invert (switched polarity) 45 runs/h. Since the three strategies developed are statistically equivalent, Mush was selected due to the higher analytical frequency in comparison with the other methods. A few figures of merit of the proposed method include: good linearity (R(2) > 0.9999); limit of detection of 0.5 mg L(-1): inter-day precision better than 1.03% (n = 9) and recovery in the range of 95.1-104.5%. (C) 2009 Elsevier B.V. All rights reserved.

A dinâmica do desenvolvimento regional do meio oeste catarinense

Dissertação apresentada ao Programa de Mestrado em Administração da Universidade Municipal de São Caetano do Sul - USCS

O estilo gerencial do executivo público catarinense

The purpose of this study was make an utterance of the managerial style of the public executive from Santa Catarina and compare it with public executives from Minas Gerais and United States, considering their capacity in giving and receiving feedback and their opening or auto-expositions in the interrelations with subordinates. It began with a review of the literature about functions and managerial style from several contributions that exist in the theory of the organizations. The theoric countersignement used in this essay was stablished in “Johari’s Window”, of Luft, that brought the possibility of the analysis of the interpersonal relations, considering the feedback variants and opening. The research is descriptive and still comparative, being applied to public executives from Santa Catarina, between the occupants of the first and the second hierarchic rungs. The instrument used was the questionnaire “Personel Relations Surwey”, of John Hall and Martha Williams, the same was applied at the researches that had been made in Minas Gerais and in United States. It was evident, by the statistic analysis in coherence with the theoric model, several conclusions, among them we detach: a) The unexistence of a standart managerial style between public executives from Santa Catarina; b) Executives from this state use more feedback than executives from Minas Gerais and the same as north-americans; c) The executives from Santa Catarina have more opening (overture) than mineiros and north-americans; d) Some personel variants interfere in the managerial style of the public executive from Santa Catarina.

A produção como vantagem competitiva : aplicação de um modelo de diagnóstico para formulação de uma estratégia de produção em uma empresa agroindustrial

Esta pesquisa, dentro de suas limitações, procurou ser uma contribuição à abordagem na qual a manufatura é vista como um elemento ativo na estratégia de negócio de uma determinada empresa, atuando ora como suporte à estratégia competitiva, ou sendo a própria fonte de vantagem competitiva. Para isso foi realizado um estudo de caso na Campeiro Produtos Alimentícios Ltda., empresa agroindustrial do setor arrozeiro, localizada em Tubarão, Santa Catarina, com o objetivo de responder à seguinte questão de pesquisa: Em quais critérios competitivos a Campeiro Produtos Alimentícios Ltda. pode focalizar seus recursos para que a produção seja uma fonte de vantagem competitiva, com vistas à formulação e implementação de uma estratégia de produção? A justificativa para realização desta pesquisa foi o fato de a produção ser apresentada como chave para o sucesso de empresas deste segmento, segundo vários empresários, e por não se verificar clareza de como a função produção pode aumentar a competitividade, assim como não se encontram na literatura metodologias adaptadas, nem informações sobre critérios competitivos para o setor. Outro aspecto é que as empresas tratam o mercado de forma homogênea, desconsiderando as possíveis variações que os segmentos possam apresentar e, dessa forma, negligenciando suas necessidades, com possível perda de competitividade. Assim, foi necessário: identificar na literatura as possíveis dimensões competitivas com as quais uma empresa pode competir e subdividi-las em critérios específicos; através de entrevistas em profundidade identificar possíveis critérios competitivos relevantes para o segmento ao qual pertence a Campeiro Produtos Alimentícios Ltda.; identificar quais são os critérios mais importantes; identificar comparativamente aos concorrentes, o desempenho da empresa, nesses diversos critérios; e identificar, por meio da matriz importância-desempenho, quais as dimensões competitivas em que a empresa poderia focalizar seus esforços para que a produção se torne uma fonte de vantagem competitiva. Os resultados possibilitaram identificar novos critérios competitivos específicos do setor agroindustrial, como por exemplo: garantia de entrega ao longo do ano e garantia de entrega no preço cotado, atribuídos a sazonalidade de produção. Permitiram também perceber quais os critérios competitivos mais importantes e qual a prioridade para cada segmento, verificar as incoerências de seu posicionamento estratégico atual e discutir a possibilidade de a empresa competir em todos os segmentos.

Modelamento geomecânico para o dimensionamento de pilares de carvão

O dimensionamento de pilares em mineração de carvão, no Brasil, sempre foi considerado conservativo em relação às metodologias e características das camadas que estava sendo lavrada. Torna-se necessário reverter o status-quo existente nesse tema para que a atividade de mineração em carvão se torne mais lucrativa e segura ao mesmo tempo. Problemas geomecânicos, que causaram acidentes fatais, diminuição das reservas de carvão, alto custo de extração e baixa recuperação na lavra são decorrentes ao baixo conhecimento do comportamento geomecânico do maciço rochoso e das metodologias de modelamento geomecânicos. Esse trabalho propõe uma nova técnologia de mapeamento geomecânico e caracterização geomecânica para determinar parâmetros geomecânicos das rochas que formam o sistema piso-pilarteto de uma camada de carvão. O dimensionamento de pilares, então, deve ser baseado nessas informações que alimentam um modelo geomecânico que utiliza métodos numéricos para solucionálos. Dentro do processo de aquisição de informações geomecânicas são propostos novos métodos de mapeamento geomecânico por janela amostral e o cálculo dos índices espaçamento médio e freqüência de descontinuidades. Baseado nas características quantitativas das descontinuidades é proposto o cálculo do RQD* (Rock Quality Designation teórico) para a camada de carvão com base na função de distribuição que se ajusta ao histograma de distribuição do espaçamento de descontinuidades. Esse procedimento refletiu melhor a qualidade do maciço rochoso, baseado no índice RMR (Rock Mass Rating). Considerando-se a qualidade do maciço rochoso e utilizando critérios de rupturas empíricos, foram estimados os parâmetros geomecânicos das rochas que alimentaram os modelos geomecânicos.(Continua)_ Foram gerados modelos numéricos para simular situações reais encontradas na camada Bonito em Santa Catarina e propor um novo paradigma para dimensionamento de pilares, baseado em simulação numérica, considerando todo o entorno do pilar, compreendendo o sistema piso-pilarteto. Os resultados desses modelos são comparados com o monitoramento das deformações dos pilares para confrontar as simulações numéricas com o comportamento geomecânico do maciço insitu. Os resultados apresentaram grande qualidade e concordância com o comportamento dos pilares apresentados no monitoramento das deformações, provando que a metodologia proposta aqui pode ser utilizada em futuros projetos de dimensionamento de pilares.