Glacial-interglacial temperature change in the tropical West Pacific: a comparison of stalagmite-based paleo-thermometers

In the tropics, geochemical records from stalagmites have so far mainly been used to qualitatively reconstruct changes in precipitation, but several new methods to reconstruct past temperatures from stalagmite material have emerged recently: i) liquid–vapor homogenization of fluid inclusion water ii) noble gas concentrations in fluid inclusion water, iii) the partitioning of oxygen isotopes between fluid inclusion water and calcite, and iv) the abundance of the 13C18O16O (‘clumped’) isotopologue in calcite. We present, for the first time, a direct comparison of these four paleo-thermometers by applying them to a fossil stalagmite covering nearly two glacial–interglacial cycles (Marine Isotope Stages (MIS) 12–9) and to two modern stalagmites, all from northern Borneo. The temperature estimates from the different methods agree in most cases within errors for both the old and recent samples; reconstructed formation temperatures of the recent samples match within 2-sigma errors with measured cave temperatures. However, slight but systematic deviations are observed between noble gas and liquid–vapor homogenization temperatures. Whereas the temperature sensitivity of fluid inclusion δ18O and clumped isotopes is currently debated, we find that the calibration of Tremaine et al. (2011) for fluid inclusion δ18O and a synthetic calcite-based clumped isotope calibration (Ziegler et al., in prep.) yield temperature estimates consistent with the other methods. All methods (with the potential exception of clumped isotopes) show excellent agreement on the amplitude of glacial–interglacial temperature change, indicating temperature shifts of 4–5 °C. This amplitude is similar to the amplitude of Mg/Ca-based regional sea surface temperature records, when correcting for sea level driven changes in cave elevation. Our reconstruction of tropical temperature evolution over the time period from 440 to 320 thousand years ago (ka) adds support to the view that climate sensitivity to varying greenhouse forcing is substantial also in the deep tropics.

Shakespeare: from author to audience to print, 1608-1616

This essay analyses the transmission of the texts of Shakespeare's final plays, Pericles, Coriolanus, Cymbeline, The Winter’s Tale, The Tempest, Henry VIII and The Two Noble Kinsmen, from author to censor to stage to print and argues that he had refined his writing, revision and collaborative practices.

Comparison of SERS performances of Co and Ni ultrathin films over silver to electrochemically activated Co and Ni electrodes

In this work, the surface-enhanced Raman scattering (SERS) spectra of pyridine (py) on thin films of Co and Ni electrodeposited on an Ag electrode activated by oxidation-reduction cycles (ORC) are presented. The SERS spectra from the thin films were compared to those of py on activated bare transition metal electrodes. It was verified that the SERS spectra of py on 3 monolayers (ML)-thick films of Ni and Co presented only bands assignable to the py adsorbed on transition metal surfaces. It was also observed that even for 50 ML-thick transition metal films, the py SERS intensity was ca. 40% of the intensity from the 3 ML-thick films. The relative intensities of the SERS bands depended on the thickness of the films, and for films thicker than 7 ML for Co and 9 ML for Ni they were very similar to those of the bare transition metal electrodes. The transition metal thin films over Ag activated electrodes presented SERS intensities 3 orders of magnitude higher than the ones from bare transition metal electrodes. These films are more suitable to study the adsorption of low Raman cross-section molecules than are ORC-activated transition metal electrodes.

Temperature (over) compensation in an oscillatory surface reaction

Biological rhythms are regulated by homeostatic mechanisms that assure that physiological clocks function reliably independent of temperature changes in the environment. Temperature compensation, the independence of the oscillatory period on temperature, is known to play a central role in many biological rhythms, but it is rather rare in chemical oscillators. We study the influence of temperature on the oscillatory dynamics during the catalytic oxidation of formic acid on a polycrystalline platinum electrode. The experiments are performed at five temperatures from 5 to 25 degrees C, and the oscillations are studied under galvanostatic control. Under oscillatory conditions, only non-Arrhenius behavior is observed. Overcompensation with temperature coefficient (q(10), defined as the ratio between the rate constants at temperature T + 10 degrees C and at T) < I is found in most cases, except that temperature compensation with q(10) approximate to I predominates at high applied currents. The behavior of the period and the amplitude result from a complex interplay between temperature and applied current or, equivalently, the distance from thermodynamic equilibrium. High, positive apparent activation energies were obtained under voltammetric, nonoscillatory conditions, which implies that the non-Arrhenius behavior observed under oscillatory conditions results from the interplay among reaction steps rather than, from a weak temperature dependence of the individual steps.

Modelling water adsorption on Au(210) surfaces: II. Monte Carlo simulations

Canonical Monte Carlo simulations for the Au(210)/H(2)O interface, using a force field recently proposed by us, are reported. The results exhibit the main features normally observed in simulations of water molecules in contact with different noble metal surfaces. The calculations also assess the influence of the surface topography on the structural aspects of the adsorbed water and on the distribution of the water molecules in the direction normal to the metal surface plane. The adsorption process is preferential at sites in the first layer of the metal. The analysis of the density profiles and dipole moment distributions points to two predominant orientations. Most of the molecules are adsorbed with the molecular plane parallel to surface, while others adsorb with one of the O-H bonds parallel to the surface and the other bond pointing towards the bulk liquid phase. There is also evidence of hydrogen bond formation between the first and second solvent layers at the interface. (c) 2007 Elsevier B.V. All rights reserved.

Cobalt catalysts derived from hydrotalcite-type precursors applied to steam reforming of ethanol

Catalysts derived from Co/Mg/Al hydrotalcite-type precursors modified with La and Ce were characterized by XANES and tested in ethanol steam reforming. The reaction data showed that, with a molar ratio of water: ethanol = 3:1 in the feed, addition of Ce and La favored acetaldehyde production. Increasing the water content (water:ethanol = 5:1) decreased the acetaldehyde formation by favoring the adsorption of water molecules on these samples, enhancing the acetaldehyde conversion. (C) 2011 Elsevier B.V. All rights reserved.

Methane conversion reactions on Ni catalysts promoted with Rh: Influence of support

Ni catalysts supported on gamma-Al(2)O(3) and Mg(Al)O were prepared with and without Rh as a promoter and tested in the reforming of methane in the presence of excess methane, simulating a model biogas. The effects of adding synthetic air on the methane conversion and the formation of carbon were assessed. The catalysts were characterized by X-ray spectroscopy (EDS), surface area (BET), X-ray diffraction (XRD), Temperature-programmed reduction (TPR), X-ray absorption near-edge structure (XANES) and XPD. The results showed that in catalysts without Rh, the Ni interacts strongly with the supports, showing high reduction temperatures in TPR tests. The addition of Rh increased the amount of reducible Ni and facilitated the reduction of the species interacting strongly with the support. In the catalytic tests, the samples promoted with Rh suffered higher carbon deposition. The in situ XPD suggested that on the support gamma-Al(2)O(3), the presence of Rh probably led to a segregation of Ni species with time on stream, leading to carbon deposition. On the support MgAlO, the presence of Rh improved the dispersion of Ni, by reducing the Ni(0) crystallite size, suggesting that in this case the carbon deposition was due to a favoring of CH(4) decomposition by Rh. (C) 2011 Elsevier B.V. All rights reserved.

Activation Energies of the Electrooxidation of Formic Acid on Pt(100)

The electrooxidation of small organic molecules on platinum surfaces usually involves different structure-dependent steps that include adsorption and desorption of various species and multiple reaction pathways. Because temperature plays a decisive role on each individual step, understanding its global influence on the reaction mechanism is often a difficult task, especially when the system is studied under far from equilibrium conditions in the presence of kinetic instabilities. Aiming at contributing to unravel this problem, herein, we report an experimental study of the role played by temperature on the electrooxidation of formic acid on a Pt(100) electrode. The system was investigated under both close and far from equilibrium conditions, and apparent activation energies were estimated using different strategies. Overall, comparable activation energies were estimated under oscillatory and quasi-stationary conditions, at high potentials. At low potentials, the poisoning process associated with the formic acid dehydration step presented a negligible dependence with temperature and, therefore, zero activation energy. On the basis of our experimental findings, we suggest that formic acid dehydration is the main, but maybe not the unique, step that differentiates the temperature dependence of the oscillatory electrooxidation of formic acid on Pt(100) with that on polycrystalline platinum.

A theoretical study on the XeF(2) molecule

A relativistic four-component study was performed for the XeF(2) molecule by using the Dirac-Coulomb (DC) Hamiltonian and the relativistic adapted Gaussian basis sets (RAGBSs). The comparison of bond lengths obtained showed that relativistic effects on this property are small (increase of only 0.01 angstrom) while the contribution of electron correlation, obtained at CCSD(T) or CCSD-T levels, is more important (increase of 0.05 angstrom). Electron correlation is also dominant over relativistic effects for dissociation energies. Moreover, the correlation-relativity interaction is shown to be negligible for these properties. The electron affinity, the first ionization potential and the double ionization potential are obtained by means of the Fock-space coupled cluster (FSCC) method, resulting in DC-CCSD-T values of 0.3 eV, 12.5 eV and 32.3 eV, respectively. Vibrational frequencies and some anharmonicity constants were also calculated under the four-component formalism by means of standard perturbation equations. All these molecular properties are, in general, ill satisfactory agreement with available experimental results. Finally, a partition in terms of charge-charge flux-dipole flux (CCFDF) contributions derived by means of the quantum theory of atoms in molecules (QTAIM) in non-relativistic QCISD(FC)/3-21G* calculations was carried out for XeF(2) and KrF(2). This analysis showed that the most remarkable difference between both molecules lies on the charge flux contribution to the asymmetric stretching mode, which is negligible in KrF(2) but important in XeF(2). (c) 2008 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).

Bordering on Disaster?

Borders, the bookstore, provides us with an instructive case study regarding our collective futures. While Amazon and Barnes & Noble made changes that both streamlined and changed their services, Borders followed the “business as usual” model. That led to Chapter 11, the closing of nearly a third of their stores, and a complete restructuring of all that’s left. Not many industry analysts think even this will be enough to keep the company afloat.

Formação da estratégia de marketing : a construção de um modelo teórico

Esta tese aborda o tema estratégia de marketing, enfocando sua formulação e implementação. Seus objetivos estão centrados no desenvolvimento de um modelo teórico de formação da estratégia de marketing, apresentando e definindo os elementos e as inter-relações necessárias para as empresas construírem e desenvolverem estratégias de marketing, bem como os antecedentes e resultados do processo da estratégia. A fim de atingir tais objetivos, elaborou-se um método que cumpre duas etapas: uma pesquisa exploratória e qualitativa e outra pesquisa descritiva e quantitativa. A etapa exploratória contempla a construção de um Modelo Conceitual Teórico preliminar, a partir de revisão bibliográfica, baseando-se especialmente em dois modelos de formação da estratégia de marketing, o de Menon et al. (1999) e o de Noble e Mokwa (1999), e de entrevistas em profundidade com executivos. A etapa descritiva, por sua vez, constitui-se de pesquisa em 200 empresas brasileiras, aplicando questionário construído e testado na etapa anterior, com a finalidade de validar o construto inicialmente construído, através da Modelagem de Equações Estruturais. A análise dos resultados da pesquisa demonstrou as variáveis significativas, bem como as suas relações para a construção do modelo de formação da estratégia de marketing. Neste modelo, verificou-se que os antecedentes da estratégia são formados por cultura organizacional inovadora e importância da estratégia. O processo de formulação e implementação é composto por comprometimento, comunicação e integração dos grupos de trabalho, alternativas estratégicas e ativos e competências organizacionais. Os resultados deste processo correspondem ao desenvolvimento de aprendizagem organizacional e de criatividade, como também, ao desempenho financeiro e de mercado. A inter-relação dessas variáveis resulta no modelo de formação da estratégia de marketing. Ainda, constatou-se que este modelo sofre influência de um ambiente externo turbulento, bem como do poder dos intermediários. Por fim, esta pesquisa colabora para o desenvolvimento da área de marketing no país, ao construir um modelo teórico para a formulação e implementação de estratégias, a partir da realidade empresarial brasileira.

Dietas de proteína reduzida e de diferentes digestabilidades suplementadas com aminoácidos sintéticos para frangos de corte

O conceito de proteína ideal adquiriu grande importância, devido à necessidade de maximizar o uso dos aminoácidos para a deposição de proteína corporal. O objetivo deste trabalho foi avaliar a formulação de rações com teor reduzido de PB suplementadas com aminoácidos sintéticos e de diferentes digestibilidades. Foram realizados dois experimentos (exp) utilizando frangos de corte machos das linhagens Ross (exp I) e Cobb (exp 11),no período de 3 a 6 semanas. No exp I foram testadas rações à base de milho e farelo de soja com quatro níveis de PB (20,8; 19,7; 18,6 e 17,5%). No exp 11,além dos tratamentos com os mesmos níveis de PB do exp I e digestibilidade padrão (DP), compostos principalmente por milho e farelo de soja, também foram testados dois tratamentos com dietas contendo 20,8 e 17,5% de PB e alta digestibilidade (AD), à base de milho, farelo de soja, amido de milho e proteína isolada de soja. Nos dois experimentos o ganho de peso, a conversão alimentar e o rendimento de cortes nobres foram negativamente afetados pela redução da PB dietética (P<0,05). Entretanto, as respostas de digestibilidade da matéria seca e digestibilidade da matéria orgânica, a retenção relativa de PB e a energia metabolizável aparente corrigida para nitrogênio foram superiores nas aves alimentadas com as dietas de baixos níveis de PB (P<0,05), mas não suficientes para compensar as perdas no desempenho. Não houve efeito da dieta AD sobre as respostas avaliadas, talvez em função das características físicas dos ingredientes utilizados.

Análise dos fatores para implantação de estratégias na perspectiva de gerentes de nivel médio de um grande banco nacional

No campo de “Estratégia Empresarial”, diversos estudos dos anos 1990 e 2000 tratam de como as estratégias devem ser formuladas para garantir o sucesso das organizações. Porém, nesse mesmo período, apenas alguns deles se debruçaram sobre o tema modelos e obstáculos na implantação das estratégias. Considerando que os gerentes médios são parte fundamental no sucesso da implantação das estratégias organizacionais, essa dissertação tem como objeto identificar o que motiva e influencia a atuação desses profissionais na condução da equipe e assimilação das diretrizes da empresa. Por meio de entrevistas estruturadas com gerentes médios de um grande banco nacional, esse trabalho apresenta uma investigação empírica e identifica os pontos de convergência e divergência dos entrevistados com a literatura de implantação de estratégia. Retomando as pesquisas de Hornsby (2002), Okumus (2001), Noble (1999), Littler (2000) entre outros autores, verificou-se que a visão dos gerentes médios converge e aprofunda os pontos apresentados na literatura como fundamentais na implantação das estratégias tais como: comunicação transacional, frequente, descentralizada; processos de implantação mais abrangentes, com abordagem qualitativa; alta gestão mais participativa na execução das estratégias, ambiente favorável a mudança, possibilidade de se assumir riscos e definição clara dos papéis e dos ganhos de cada membro no projeto.

Análise dos fatores para implantação de estratégias na perspectiva de gerentes de nível médio de um grande banco nacional

No campo de “Estratégia Empresarial”, diversos estudos dos anos 1990 e 2000 tratam de como as estratégias devem ser formuladas para garantir o sucesso das organizações. Porém, nesse mesmo período, apenas alguns deles se debruçaram sobre o tema modelos e obstáculos na implantação das estratégias. Considerando que os gerentes médios são parte fundamental no sucesso da implantação das estratégias organizacionais, essa dissertação tem como objeto identificar o que motiva e influencia a atuação desses profissionais na condução da equipe e assimilação das diretrizes da empresa. Por meio de entrevistas estruturadas com gerentes médios de um grande banco nacional, esse trabalho apresenta uma investigação empírica e identifica os pontos de convergência e divergência dos entrevistados com a literatura de implantação de estratégia. Retomando as pesquisas de Hornsby (2002), Okumus (2001), Noble (1999), Littler (2000) entre outros autores, verificou-se que a visão dos gerentes médios converge e aprofunda os pontos apresentados na literatura como fundamentais na implantação das estratégias tais como: comunicação transacional, frequente, descentralizada; processos de implantação mais abrangentes, com abordagem qualitativa; alta gestão mais participativa na execução das estratégias, ambiente favorável a mudança, possibilidade de se assumir riscos e definição clara dos papéis e dos ganhos de cada membro no projeto