Disruption of Saccharomyces cerevisiae by Plantaricin 149 and investigation of its mechanism of action with biomembrane model systems

The action of a synthetic antimicrobial peptide analog of Plantaricin 149 (Pln149a) against Saccharomyces cerevisiae and its interaction with biomembrane model systems were investigated. Pln149a was shown to inhibit S. cerevisiae growth by more than 80% in YPD medium, causing morphological changes in the yeast wall and remaining active and resistant to the yeast proteases even after 24 h of incubation. Different membrane model systems and carbohydrates were employed to better describe the Pln149a interaction with cellular components using circular dichroism and fluorescence spectroscopies, adsorption kinetics and surface elasticity in Langmuir monolayers. These assays showed that Pln149a does not interact with either mono/polysaccharides or zwitterionic LUVs, but is strongly adsorbed to and incorporated into negatively charged surfaces, causing a conformational change in its secondary structure from random-coil to helix upon adsorption. From the concurrent analysis of Pln149a adsorption kinetics and dilatational surface elasticity data, we determined that 2.5 mu M is the critical concentration at which Pln149a will disrupt a negative DPPG monolayer. Furthermore, Pln149a exhibited a carpet-like mechanism of action, in which the peptide initially binds to the membrane, covering its surface and acquiring a helical structure that remains associated to the negatively charged phospholipids. After this electrostatic interaction, another peptide region causes a strain in the membrane, promoting its disruption. (C) 2009 Elsevier B.V. All rights reserved.

Spectroscopic and structural studies of bis[isopropoxy(thiocarbonyl)]sulfide, [(CH(3))(2)CHOC(S)](2)S

Structural and conformational properties of the molecule bis[isopropoxy(thiocarbonyl)]sulfide, [(CH(3))(2)CHOC(S)](2)S, have been studied by vibrational spectroscopy (IR and Raman) and quantum chemical calculations (HF and B3LYP with 6-31+G* basis sets). The crystal and molecular structure of the title compound was determined by X-ray diffraction methods. It crystallizes in the monoclinic C2/c space group with a = 8.4007(4), b = 13.5936(5), c = 10.3648(5) angstrom, beta = 106.024(4)degrees and Z = 4 molecules per unit cell. The molecules are sited on a crystallographic twofold axis passing through the sulphide atom and arranged in layers perpendicular to the b-axis. The solid state IR and Raman spectra of the compound give no sign of any other rotamer. (C) 2009 Elsevier B.V. All rights reserved.

Structural effects and hydrogen bonds on N,N `-di(methoxycarbonylsulfenyl)urea, [CH(3)OC(O)SNH](2)CO, studied by experimental and theoretical methods

Pure N,N`-di(methoxycarbonylsulfenyl)urea, [CH(3)OC(O)SNH](2)CO, is quantitatively prepared by the hydrolysis reaction of CH(3)OC(O)SNCO and characterized by (1)H NMR, GC-MS and FTIR spectroscopy techniques. Structural and conformational properties are analyzed using a combined approach with data obtained from X-ray diffraction, vibrational spectra and theoretical calculation methods. The IR and Raman spectra for normal and deuterated species are reported. The crystal structure of [CH(3)OC(O)SNH](2)CO was determined by X-ray diffraction methods. The substance crystallizes in the orthorhombic P2(1)2(1)2 space group with a = 9.524(2), b = 12.003(1), c = 4.481 (1) angstrom, and Z = 2 moieties in the unit cell. The molecule is sited on a twofold crystallographic axis (C(2)) parallel to c and shows the anti-anti conformation (S-N single bonds antiperiplanar with respect to the opposite C-N single bonds in sulfenyl-urea-sic group). Neighboring molecules are arranged in a chain motif that extends along the C(2)-axis and is held by bifurcated NH center dot center dot center dot O center dot center dot center dot HN intermolecular bonds. A local planar symmetry is observed in the crystal for the central -SN(H)C(O)N(H)S- skeleton. Experimental and calculated data allow to trace this structural feature to the occurrence of N-H center dot center dot center dot O=C hydrogen bonding interactions. Calculated vibrational and structural properties are in good agreement with the experimentally determined features. (C) 2008 Elsevier B.V. All rights reserved.

Tetrachlorocarbonyliridates: Water-Soluble Carbon Monoxide Releasing Molecules Rate-Modulated by the Sixth Ligand

A new family of compounds is presented as potential carbon monoxide releasing molecules (CORMs). These compounds, based on tetrachlorocarbonyliridate(III) derivatives, were synthesized and fully characterized by X-ray diffraction, electrospray mass spectrometry, IR. NMR, and density functional theory calculations. The rate of CO release was studied via the myoglobin assay. The results showed that the rate depends on the nature of the sixth ligand, trans to CO, and that a significant modulation on the release rate can be produced by changing the ligand. The reported compounds are soluble in aqueous media, and the rates of CO release are comparable with those for known CORMs, releasing CO at a rate of 0.03-0.58 mu M min(-1) in a 10 mu M solution of myoglobin and 10 mu M of the complexes.

Synthesis, molecular structure and physicochemical properties of bis(3 `-azido-3 `-deoxythymidin-5 `-yl) carbonate

3`-Azido-3`-deoxythymidine (zidovudine, AZT), a synthetic analog of natural nucleoside thymidine, has been used extensively in AIDS treatments. We report here the synthesis. X-ray crystal and molecular structure, NMR, IR and Raman spectra and the thermal behavior of a novel carbonate of AZT [(AZT-O)(2)C=O], prepared by the reaction of zidovudine with carbonyldiimidazole. The carbonate compound, C(21)H(24)N(10)O(9), crystallizes in the tetragonal space group P4(1)2(1)2 with a = b = 15.284(1), c = 21.695(1) angstrom, and Z = 8 molecules per unit cell. It consists of two AZT moieties of closely related conformations which are bridged by a carbonyl group to adopt a folded Z-like shape. (C) 2010 Elsevier B.V. All rights reserved.

High T/P evolution and metamorphic ages of the migmatitic basement of northern Sierras Pampeanas, Argentina: Characterization of a mid-crustal segment of the Famatinian belt

New petrologic, thermobarometric and U-Pb monazite geochronologic information allowed to resolve the metamorphic evolution of a high temperature mid-crustal segment of an ancient subduction-related orogen. The EI Portezuelo Metamorphic-Igneous Complex, in the northern Sierras Pampeanas, is mainly composed of migmatites that evolved from amphibolite to granulite metamorphic facies, reaching thermal peak conditions of 670-820 degrees C and 4.5-5.3 kbar. The petrographic study combined with conventional and pseudosection thermobarometry led to deducing a short prograde metamorphic evolution within migmatite blocks. The garnet-absent migmatites represent amphibolite-facies rocks, whereas the cordierite-garnet-K-feldspar-sillimanite migmatites represent higher metamorphic grade rocks. U-Pb geochronology on monazite grains within leucosome record the time of migmatization between approximate to 477 and 470 Ma. Thus, the El Portezuelo Metamorphic-Igneous Complex is an example of exhumed Early Ordovician anatectic middle crust of the Famatinian mobile belt. Homogeneous exposure of similar paleo-depths throughout the Famatinian back-arc and isobaric cooling paths suggest slow exhumation and consequent longstanding crustal residence at high temperatures. High thermal gradients uniformly distributed in the Famatinian back-arc can be explained by shallow convection of a low-viscosity asthenosphere promoted by subducting-slab dehydration. (C) 2011 Elsevier Ltd. All rights reserved.

Tectonothermal evolution and exhumation history of the Paleozoic Proto-Andean Gondwana margin crust: The Famatinian Belt in NW Argentina

We studied the P-T-t evolution of a mid-crustal igneous-metamorphic segment of the Famatinian Belt in the eastern sector of the Sierra de Velasco during its exhumation to the upper crust. Thermobarometric and geochronological methods combined with field observations permit us to distinguish three tectonic levels. The deepest Level I is represented by metasedimentary xenoliths and characterized by prograde isobaric heating at 20-25 km depth. Early/Middle Ordovician granites that contain xenoliths of Level I intruded in the shallower Level II. The latter is characterized by migmatization coeval with granitic intrusions and a retrograde isobaric cooling P-T path at 14-18 km depth. Level II was exhumed to the shallowest supracrustal Level III, where it was intruded by cordierite-bearing granites during the Middle/Late Ordovician and its host-rock was locally affected by high temperature-low pressure HT/LP metamorphism at 8-10 km depth. Level III was eventually intruded by Early Carboniferous granites after long-term slow exhumation to 6-7 km depth. Early/Middle Ordovician exhumation of Level II to Level III (Exhumation Period I,0.25-0.78 mm/yr) was faster than exhumation of Level III from the Middle/Late Ordovician to the Lower Carboniferous (Exhumation Period II, 0.01-0.09 mm/yr). Slow exhumation rates and the lack of regional evidence of tectonic exhumation suggest that erosion was the main exhumation mechanism of the Famatinian Belt. Widespread slow exhumation associated with crustal thickening under a HT regime suggests that the Famatinian Belt represents the middle crust of an ancient Altiplano-Puna-like orogen. This thermally weakened over-thickened Famatinian crust was slowly exhumed mainly by erosion during similar to 180 Myr. (C) 2010 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Evaluation of petrogenetic models for intermediate and silicic plutonic rocks from the Sierra de Valle Fertil-La Huerta, Argentina: Petrologic constraints on the origin of igneous rocks in the Ordovician Famatinian-Puna paleoarc

The whole Valle Fertil-La Huerta section appears as a calc-alkaline plutonic suite typical of a destructive plate margin. New Sr and Nd isotopic whole-rock data and published whole-rock geochemistry suggest that the less-evolved intermediate (dioritic) rocks can be derived by magmatic differentiation, mainly by hornblende + plagioclase +/- Fe-Ti oxide fractional crystallization, from mafic (gabbroic) igneous precursors. Closed-system differentiation, however, cannot produce the typical intermediate (tonalitic) and silicic (granodioritic) plutonic rocks, which requires a preponderant contribution of crustal components. Intermediate and silicic plutonic rocks from Valle Fertil-La Huerta section have formed in a plate subduction setting where the thermal and material input of mantle-derived magmas promoted fusion of fertile metasedimentary rocks and favored mixing of gabbroic or dioritic magmas with crustal granitic melts. Magma mixing is observable in the field and evident in variations of chemical elemental parameters and isotopic ratios, revealing that hybridization coupled with fractionation of magmas took place in the crust. Consideration of the whole-rock geochemical and isotopic data in the context of the Famatinian-Puna magmatic belt as a whole demonstrates that the petrologic model postulated for the Sierra Valle Fertil-La Huerta section has the potential to explain the generation of plutonic and volcanic rocks across the Early Ordovician paleoarc from central and northwestern Argentina. As the petrologic model does not require the intervention of old Precambrian continental crust, the nature of the basement on which thick accretionary turbiditic sequences were deposited remains a puzzling aspect. Discussion in this paper provides insights into the nature of magmatic source rocks and mechanisms of magma generation in Cordilleran-type volcano-plutonic arcs of destructive plate margins. (C) 2010 Elsevier Ltd. All rights reserved.

Post-collisional lamprophyric event in Sierra Norte, Cordoba, Argentina: Mineralogical, geochemical and isotopic characteristics

Over 20 lamprophyre dykes, varying in width between a few centimeters and several meters, have been identified in central Sierra Norte - Eastern Pampean Ranges, Cordoba, Argentina. Their mineralogy and chemistry indicate that they are part of the calc-alkaline lamprophyres clan (CAL). They contain phenocrysts of magnesiohomblende +/- augite set in a groundmass of magnesiohornblende, calcic-plagioclase, alkali feldspar, and opaque minerals, which designate them as spessartite-type lamprophyres. Alteration products include chlorite, calcite and iron oxides after malfic phenocrysts, though some are partially replaced by actinolite. Feldspars are replaced by carbonate and clay minerals. The dykes are relatively primitive, and show restricted major element variation (SiO(2) 51.1-55.3 wt.%, Al(2)O(3) 12-16.6 wt.%, total alkalies 1.5-4.7 wt.%), high Mg# (55-77), high Cr contents (27-988 ppm) and moderate to high Ni contents (60-190 ppm). Lamprophyre LILE (e.g. Rb averages 110 ppm, Sr 211-387 ppm, Ba 203-452 ppm) are high relative to HFSE (e.g., Ta 0.2-1.6 ppm, Nb 4-11 ppm, Y 17-21 ppm), and are enriched in LREE (30-70 times chondrite). They are characterized by relatively high (208)Pb/(204)Pb (38.8-39.9), (207)Pb/(204)Pb(similar to 15.7), and (206)Pb/(204)Pb (18.7-20.1), combined with low (epsilon)epsilon(Nd) (-4.69 to -1.52) and a relative moderately high ((87)Sr/(86)Sr)(i) of 0.7055-0.7074. The Rb-Sr whole rock isochron indicates an Early Ordovician age of 485 +/- 25 Ma. The calculated T(DM) (1.7 Ga) suggests that these rocks appear to have originated from a reservoir that was created during a mantle metasomatism event related to the Pampean orogeny. The Sierra Norte lamprophyres show affinities with a subduction-related magma in an active continental margin. Their geochemical and isotopic features suggest a multicomponent source, composed of enriched mantle material variably contaminated by crustal components. The lamprophyric suite emplacement occurred at the dawning stage of the Pampean orogeny, in a regional post-collisional extensional setting developed in the Sierra Norte-Ambargasta batholith (SNAB) in Early Ordovician times. (C) 2008 Published by Elsevier Ltd.

pH-Sensitive Binding of Cytochrome c to the Inner Mitochondrial Membrane. Implications for the Participation of the Protein in Cell Respiration and Apoptosis

Cytochrome c exhibits two positively charged sites: site A containing lysine residues with high pK(a) values and site L containing ionizable groups with pK(aobs),values around 7.0. This protein feature implies that cytochrome c can participate in the fusion of mitochondria and have its detachment from the inner membrane regulated by cell acidosis and alkalosis. In this study, We demonstrated that both horse and tuna cytochrome c exhibited two types of binding to inner mitochondrial membranes that contributed to respiration: a high-affinity and low-efficiency pi-I-independent binding (microscopic dissociation constant K(sapp2), similar to 10 nM) and a low-affinity and high-efficiency pH-dependent binding that for horse cytochrome c had a pK(a) of similar to 6.7. For tuna cytochrome c (Lys22 and His33 replaced with Asn and Trp, respectively), the effect of pH on K(sapp1), was less striking than for the horse heme protein, and both tuna and horse cytochrome c had closed K(sapp1) values at pH 7.2 and 6.2, respectively. Recombinant mutated cytochrome c H26N and H33N also restored the respiration of the cytochrome c-depleted mitoplast in a pH-dependent manner. Consistently, the detachment of cytochrome c from nondepleted mitoplasts was favored by alkalinization, suggesting that site Lionization influences the participation of cytochrome c in the respiratory chain and apoptosis.

Governança Corporativa: Estrutura de Propriedade e o Valor da Empresa

A estrutura da maioria das modernas empresas está baseada na separação entre propriedade e controle. Os processos de decisão dessas empresas baseiam-se no desenho subjacente a essa estrutura, e todo este conjunto (desenho e processos) constitui o modelo de Governança Corporativa da empresa. Tal modelo implica uma série de conflitos e de assimetrias de informação, devidamente identificados na literatura de Teoria de Agencia e alargado na moderna pesquisa em Governança Corporativa. Este trabalho visa contribuir para a compreensão da relação entre os modelos de Governança Corporativa e o valor das empresas Brasileiras, medido pelo seu desempenho na Bolsa de Valores de São Paulo entre os anos de 2002 e 2006. Em particular pretende-se verificar se existe uma relação significante entre a separação propriedade / controle e o valor das empresas Brasileiras, além de se testar a linearidade desta relação.

Desafios que enfrenta a ANP para regular a indústria de petróleo no Brasil depois da quebra do monopólio em 1997 ate o ano de 2005

This work is analyzing the challenges which the National Petrol Agency is facing to regulate the Petrol industry in Brazil after the Monopoly crash in the period between 1997 until 2005. Due to the necessities of adaptation of its political strategies to the rules which determine the international economic flows, Brazil was forced to use the Economic Regulation in order to control the market. The regulation established in Brazil is not indifferent to imperfect markets. Thus can be find a conflict of interests among companies, the government and consumers within this process of regulation. The established agency does not have enough autonomy for administrating a regulation. The State with its paternalism power does not allow the agency to fulfill its function for which it was established, even though its function was established by law. A regulating policy which is clearly defined will establish a strong and independent agency with a clear limitation of its competences, avoiding divergent interpretation which prioritizes investments and promotes economic development. The agency will have the challenge to regulate the companies that enter the sector, allowing the opening of the market for new initiatives of investments which contribute to the welfare of the country and breaking at the same time the monopoly that is lead by Petrobras since 1953. Combining a stable set of rules with agility in order to adapt to changes will provide the regulator with a great decision-making power. The flexibility in the regulation will improve the correcting of the rules that were set in the beginning, being more efficient, which are based on acquired experience and achieved results. The structure of the agency and the flexibility of the regulation should be orientated on the promotion of competition in order to achieve economic and social development.

Aparência e poder : novas sociabilidades urbanas, em Florianópolis, de 1950-1970

Investiga a pertinência de considerar a configuração social contemporânea como sendo uma sociedade de Moda, na qual os sujeitos sociais são desencaixados de suas experiências diretas e reencaixados por imagens, que os significam. O maior significante dessas imagens encontra-se no novo, e a sua manipulação permeia a busca de ser um outro, para qualificar o mesmo. Analisa as transformações que Florianópolis passou entre os anos de 1950 a 1970, evidenciando a busca da modernidade como meio de assemelhar-se a outras cidades consideradas modernas, especialmente, o Rio de Janeiro. Apresenta tal historicidade como processo de emersão, tendo em vista que, os discursos propaladores da cidade moderna, foram considerados centrais na constituição da imagem de Florianópolis “realizada”. Analisa a constituição da poética moderna da aparência, ressaltando o papel da publicidade, lato sensu, na instituição dos padrões de elegância e beleza e seus vínculos com a estratificação social. Salienta a presença da cultura francesa na instituição desses padrões e relaciona-os a reconversão das elites contemporâneas. Investiga os processos de recepção da poética da aparência, no contexto florianopolitano, destacando a ação do cronismo social, que agencia a manipulação de fichas simbólicas de elegância, beleza, distinção e do moderno para configurar novas formas de ser elite. As fontes são tratadas a partir da estética da recepção de Jauss. As concepções de modernidade e de suas implicações são baseadas em Marshall Berman e Anthony Giddens, especialmente. As concepções de poder partem dos pressupostos de George Balandier, entre outros. Aplica-se a definição de capital-aparência de Pagès-Delon e de reconversão social de Robert Castel e Dominique de Saint-Martin. Conclui que a positivação da aparência, numa sociedade regida pela imagem do novo, promove subjetividades que encontram no parecer sua essência de ser, isto é, instituía seres de parecer ou sujeitos-moda que, logo, estabelecem suas estratégias de poder por meio da aparência.

Análise das estratégias de entrada de mercado adotadas por uma organização privada de saúde: o caso Fleury S.A.

Esta dissertação analisa como as estratégias de entrada de mercado adotadas por uma organização privada de saúde contribuíram para a formação dos recursos e capacidades dos seus novos empreendimentos e para o desempenho desses negócios. Para tanto, este trabalho recorre a revisão bibliográfica sobre Entrada de Mercado e Teoria dos Recursos da Firma (RBV) e aplica um estudo de caso no Fleury S.A., apoiado em entrevistas semi-estruturadas com os altos executivos da organização. Os empreendimentos Check-up, Hospital-Dia e a Holding NKB são estudados em profundidade e evidenciam características distintas de entrada, que variam conforme os laços de ligação com o Fleury: por meio do crescimento interno, da formação de uma Joint Venture e da criação de uma Spin-off. Como resultados, verifica-se a convergência da literatura de Entrada de Mercado e RBV, em que os recursos e capacidades do potencial entrante têm um importante impacto no modo de entrada, bem como em sua performance pós-entrada de mercado. Por outro lado, a inexperiência no novo mercado e as analogias equivocadas foram observadas como as principais responsáveis pela entrada inapropriada em um novo mercado.

Determinantes da exploração de petróleo na indústria brasileira

Este estudo analisa os fatores que influenciaram a escolha de empresas de petróleo no Brasil a explorar os blocos licitados pela Agencia Nacional de Petróleo (ANP). Os acordos de Exploração & Produção da ANP definem um Programa Exploratório Mínimo a ser feito no bloco licitado, mas os resultados mostram que em muitos casos esse programa exploratório não foi cumprido. Os resultados empíricos mostram que vários fatores afetam a decisão de perfurar poços, entre elas o bonus final oferecido pelo bloco, a participação da Petrobras e a localização geográfica do bloco. A regulação também teve uma influência importante na exploração de blocos, pela indicação da intensidade de poços a ser perfurados e pela flexibilidade de cessão no controle dos blocos. Os resultados também mostram que novas informações têm um papel importante na decisão de perfuração, especialmente informações sobre o preço do petróleo, o prêmio pago pelo lance vencedor e as atividades prévias de perfurações em blocos vizinhos após a licitação. O estudo utiliza uma amostra de 88 blocos licitados durante as quatro primeiras rodadas de licitações da ANP e a incidência de perfurações de poços nesses blocos entre o período de 1999 a 2009.