Baroclinic stationary waves in aquaplanet models

An aquaplanet model is used to study the nature of the highly persistent low-frequency waves that have been observed in models forced by zonally symmetric boundary conditions. Using the Hayashi spectral analysis of the extratropical waves, the authors find that a quasi-stationary wave 5 belongs to a wave packet obeying a well-defined dispersion relation with eastward group velocity. The components of the dispersion relation with k ≥ 5 baroclinically convert eddy available potential energy into eddy kinetic energy, whereas those with k < 5 are baroclinically neutral. In agreement with Green’s model of baroclinic instability, wave 5 is weakly unstable, and the inverse energy cascade, which had been previously proposed as a main forcing for this type of wave, only acts as a positive feedback on its predominantly baroclinic energetics. The quasi-stationary wave is reinforced by a phase lock to an analogous pattern in the tropical convection, which provides further amplification to the wave. It is also found that the Pedlosky bounds on the phase speed of unstable waves provide guidance in explaining the latitudinal structure of the energy conversion, which is shown to be more enhanced where the zonal westerly surface wind is weaker. The wave’s energy is then trapped in the waveguide created by the upper tropospheric jet stream. In agreement with Green’s theory, as the equator-to-pole SST difference is reduced, the stationary marginally stable component shifts toward higher wavenumbers, while wave 5 becomes neutral and westward propagating. Some properties of the aquaplanet quasi-stationary waves are found to be in interesting agreement with a low frequency wave observed by Salby during December–February in the Southern Hemisphere so that this perspective on low frequency variability, apart from its value in terms of basic geophysical fluid dynamics, might be of specific interest for studying the earth’s atmosphere.

Redox control of light-induced charge separation in a transition metal cluster: photochemistry of a methyl viologen-substituted [Os-3(CO)10(a-diimine)] cluster

Sub)picosecond transient absorption (TA) and time-resolved infrared (TRIR) spectra of the cluster [OS3(CO)(10-) (AcPy-MV)](2+) (the clication AcPy-MV = Acpy-MV2+ = [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridine-1,1'-diium-1-yl) ethyl)] (PF6)(2)) (1(2+)) reveal that photoinduced electron transfer to the electron-accepting 4,4'-bipyridine-1,1'diium (MV2+) moiety competes with the fast relaxation of the initially populated sigmapi* excited state of the cluster to the ground state and/or cleavage of an Os-Os bond. The TA spectra of cluster 12 in acetone, obtained by irradiation into its lowest-energy absorption band, show the characteristic absorptions of the one-electron-reduced MV*(+) unit at 400 and 615 nm, in accordance with population of a charge-separated (CS) state in which a cluster-core electron has been transferred to the lowest pi* orbital of the remote MV2+ unit. This assignment is confirmed by picosecond TRIR spectra that show a large shift of the pilot highest-frequency nu(CO) band of 1(2+) by ca. +40 cm(-1), reflecting the photooxidation of the cluster core. The CS state is populated via fast (4.2 x 10(11) s(-1)) and efficient (88%) oxidative quenching of the optically populated sigmapi* excited state and decays biexponentially with lifetimes of 38 and 166 ps (1:2:1 ratio) with a complete regeneration of the parent cluster. About 12% of the cluster molecules in the sigmapi* excited state form long-lived open-core biradicals. In strongly coordinating acetonitrile, however, the cluster core-to-MV2+ electron transfer in cluster 12+ results in the irreversible formation of secondary photoproducts with a photooxidized cluster core. The photochemical behavior of the [Os-3(CO)(10)(alpha-diimine-MV)](2+) (donor-acceptor) dyad can be controlled by an externally applied electronic bias. Electrochemical one-electron reduction of the MV2+ moiety prior to the irradiation reduces its electron-accepting character to such an extent that the photoinduced electron transfer to MV*+ is no longer feasible. Instead, the irradiation of reduced cluster 1(.)+ results in the reversible formation of an open-core zwitterion, the ultimate photoproduct also observed upon irradiation of related nonsubstituted clusters [Os-3(CO)(10)(alpha-diimine)] in strongly coordinating solvents such as acetonitrile.

π-dimerization of pleiadiene radical cations at low temperatures revealed by UV–vis spectroelectrochemistry and quantum theory

One-electron oxidation of the non-alternant polycyclic aromatic hydrocarbon pleiadiene and related cyclohepta[ c,d]pyrene and cyclohepta[c,d]fluoranthene in THF produces corresponding radical cations detectable in the temperature range of 293–263 K only on the subsecond time scale of cyclic voltammetry. Although the EPR-active red-coloured pleiadiene radical cation is stable according to the literature in concentrated sulfuric acid, spectroelectrochemical measurements reported in this study provide convincing evidence for its facile conversion into the green-coloured, formally closed shell and, hence, EPRsilent π-bound dimer dication stable in THF at 253 K. The unexpected formation of the thermally unstable dimeric product featuring a characteristic intense low-energy absorption band at 673 nm (1.84 eV; logεmax=4.0) is substantiated by ab initio calculations on the parent pleiadiene molecule and the PF6 − salts of the corresponding radical cation and dimer dication. The latter is stabilized with respect to the radical cation by 14.40 kcal mol−1 (DFT B3LYP) [37.64 kcal mol−1 (CASPT2/DFT B3LYP)]. An excellent match has been obtained between the experimental and TDDFT- calculated UV–vis spectra of the PF6 − salt of the pleiadiene dimer dication, considering solvent (THF) effects.

Design of a biomimetic skin for an octopus-inspired robot - Part II: Development of the skin artefact

In order to develop skin artefact for an octopus-inspired robot arm, which is designed to be able to elongate 60% of its original length, silicone rubber and knitted nylon sheet were selected to manufacture an artificial skin, due to their higher elastic strain and high flexibility. Tensile and scissors cutting tests were conducted to characterise the matrix and reinforcing materials and the skin artefact. Material properties of the individual and the composite materials were compared with the measured properties of real octopus skin presented in Part I. The Young’s modulus of the skin should be below 20 MPa and the elastic strain range should be over 60%. The fracture toughness should be at least 0.9 kJ·m−2. Tubes made of the skin artefact filled with liquid were tested to study volume change under deformation. Finite element analysis model was developed to simulate the material and arm structure under tensile loading. Results show that the skin artefact developed has similar mechanical properties as the real octopus skin and satisfies all the design specifications of the OCTOPUS robot.

Enhanced MALDI MS sensitivity by weak base additives and glycerol sample coating

The concept of rationally designing MALDI matrices has been extended to the next “whole sample” level. These studies have revealed some unexpected and exploitable insights in improving MALDI sensitivity. It is shown that (i) additives which only provide additional laser energy absorption are best to be avoided; (ii) the addition of proton donors in the form of protonated weak bases can be highly beneficial; (iii) the addition of glycerol for coating crystalline samples is highly recommended. Overall, analytical sensitivity has been significantly increased compared to the current “gold” standards in MALDI MS, and new insights into the mechanisms and processes of MALDI have been gained.

Energy consistent discontinuous Galerkin methods for the Navier–Stokes–Korteweg system

We design consistent discontinuous Galerkin finite element schemes for the approximation of the Euler-Korteweg and the Navier-Stokes-Korteweg systems. We show that the scheme for the Euler-Korteweg system is energy and mass conservative and that the scheme for the Navier-Stokes-Korteweg system is mass conservative and monotonically energy dissipative. In this case the dissipation is isolated to viscous effects, that is, there is no numerical dissipation. In this sense the methods are consistent with the energy dissipation of the continuous PDE systems. - See more at: http://www.ams.org/journals/mcom/2014-83-289/S0025-5718-2014-02792-0/home.html#sthash.rwTIhNWi.dpuf

Energy consistent discontinuous Galerkin methods for a quasi-incompressible diffuse two phase flow model

We design consistent discontinuous Galerkin finite element schemes for the approximation of a quasi-incompressible two phase flow model of Allen–Cahn/Cahn–Hilliard/Navier–Stokes–Korteweg type which allows for phase transitions. We show that the scheme is mass conservative and monotonically energy dissipative. In this case the dissipation is isolated to discrete equivalents of those effects already causing dissipation on the continuous level, that is, there is no artificial numerical dissipation added into the scheme. In this sense the methods are consistent with the energy dissipation of the continuous PDE system.

Study of the spectroscopic properties and first hyperpolarizabilities of disperse azo dyes derived from 2-amino-5-nitrothiazole

The solvatochromism and other spectroscopic and photophysical characteristics of four azo disperse dyes, derived from 2-amino-5-nitrothiazole, were evaluated and interpreted with the aid of experimental data and quantum mechanical calculations. For the non-substituted compound two conformers, E and Z, were proposed for the isolated molecules, being the second one considerably less stable. The optimization of these structures in combination with a SCRF methodology (IEFPCM, Simulating the molecules in a continuum dielectric with characteristics of methanol), suggests that the Z form is not stable in solution. This same behaviour is expected for the substituted compounds, which is corroborated by experimental data presented in previous investigations [A.E.H. Machado, L.M. Rodrigues, S. Gupta, A.M.F. Oliveira-Campos, A.M.S. Silva, J. Mol. Struct. 738 (2005) 239-245]. For the substituted compounds, two forms derived from E conformer (A and R) are possible. Quantum mechanical data suggest for the isolated molecules, that the low energy absorption hand of the E conformers involve at least two close electronic states. having the low-lying excited state a (1)(n,pi*) nature, and being the S-2 state attributed to a (1)(pi,pi*) transition. The data also suggest a small energy gap between the absorption peaks of A and B, related to the easy conversion between these forms. For the structures optimized in combination with the applied SCRF methodology, an states inversion is observed for the Substituted compounds, with a considerable diminish of the energy gap between A and B absorption peaks. The electronic spectra of these compounds are quite sensitive to changes in the solvent polarity. The positive solvatochromism is more evident in aprotic solvents, probably due to the polarization induced by the solute. These compounds do not fluoresce at 298 K, but present a small but perceptible fluorescence at 77 K, which seems to be favoured by the nature of the group in the 2 `-position of the phenyl ring. Moreover, such compounds present expressive values for first hyperpolarizability, which implies in good non-linear optics (NLO) responses and photoswitching capability. (C) 2008 Elsevier B.V. All rights reserved.

Alternativas ao Crédito Rural Tradicional

The subject of the current work was to analyze the subject of the adequacy of Brazilian's agricultural activity financing model, as an alternative for the traditional agriculture credit. The main basis for this research is the evidence that the official resources for new loans, wherein it is analyzed a period within 30 years, had their highest peak in the final 70's decade and beginning of the80¿s had experimented a consistent trajectory of decline, returning to the initial levels of the final decades of the 60¿s. In parallel with the situation above, it is evidenced the increase of the Brazilian agriculture production by the official data, mainly grain plowing, followed by diverse problems like high levels of default in and continuously debt roll over, indicating depauperation from the traditional model which was institutionalized in 1965, under the Law n. 4829. A survey of official data regarding those loans, their default and field research with banks that deal with agriculture loans, from a broad Bibliographical research, ,was made in order to verify their managing strategy and willingness to use new financing mechanisms. The main proposed alternatives were: a) Cédula de Produto Rural (Rural Product Bill) b) Cédula de Produto Rural, financial modality c) Bolsa de Mercadorias e de Futuro¿s proposal d) Agricultural Receivable on Security e) Model based on Local Credit Agencies The best instrument for leveling resources were the first four alternatives, analyzing the advantages and disadvantages of each proposal. The creation of a system based on local branches for credit had not shown to be viable as for the difficulties for implementation and functioning. The work also points out a need to review the segmentation concerning rural clients. The traditional format for segmentation distinguishes 2 groups of producers: commercial agriculture and familiar agriculture. A third group is in eminence, which is the survival agriculture, with needs and distinct characteristics, indicating that the requirements for their needs must not have to be made by credit forms, but as aid programs, education and social welfare.

Ensaios sobre inflação e política monetária

Esta tese tem por objetivo principal o estudo da relação entre atividade econômica, inflação e política monetária no tocante a três aspectos importantes. O primeiro, a perspectiva histórica da evolução da relação entre atividade e inflação no pensamento econômico. O segundo, a análise da dinâmica inflacionária utilizando um modelo com fundamentação microeconômica, no caso a curva de Phillips Novo-Keynesiana, com uma aplicação ao caso brasileiro. O terceiro, a avaliação da eficiência dos mecanismos de sinalização de política monetária utilizados pelo Banco Central no Brasil com base nos movimentos na estrutura a termo da taxa de juros com a mudança da meta da Selic. O elemento central que une estes ensaios é a necessidade do formulador de política econômica compreender o impacto significativo das ações de política monetária na definição do curso de curto prazo da economia real para atingir seus objetivos de aliar crescimento econômico com estabilidade de preços. Os resultados destes ensaios indicam que o modelo Novo-Keynesiano, resultado de um longo desenvolvimento na análise econômica, constitui-se numa ferramenta valiosa para estudar a relação entre atividade e inflação. Uma variante deste modelo foi empregada para estudar com relativo sucesso a dinâmica inflacionária no Brasil, obtendo valores para rigidez da economia próximos ao comportamento observado em pesquisas de campo. Finalmente, foi aliviada a previsibilidade das ações do Banco Central para avaliar o estágio atual de desenvolvimento do sistema de metas no Brasil, através da reação da estrutura a termo de juros às mudanças na meta da taxa básica (Selic). Os resultados indicam que comparando o período de 2003 a 2008 com 2000 a 2003, verificamos que os resultados apontam para o aumento da previsibilidade das decisões do Banco Central. Este fato pode ser explicado por alguns fatores: o aprendizado do público sobre o comportamento do Banco Central; a menor volatilidade econômica no cenário econômico e o aperfeiçoamento dos mecanismos de sinalização e da própria operação do sistema de metas. Comparando-se o efeito surpresa no Brasil com aqueles obtidos por países que promoveram mudanças significativas para aumentar a transparência da política monetária no período de 1990 a 1997, observa-se que o efeito surpresa no Brasil nas taxas de curto prazo reduziu-se significativamente. No período de 2000 a 2003, o efeito surpresa era superior aos de EUA, Alemanha e Reino Unido e era da mesma ordem de grandeza da Itália. No período de 2003 a 2008, o efeito surpresa no Brasil está próximo dos valores dos EUA e Alemanha e inferiores aos da Itália e Reino Unido.

O poder dos sindicatos e a lucratividade das firmas no Reino Unido

In t-his paper an attempt is made to assess the behaviour of the rate of return on sales of unionised firms as compared to the non-unionised ones in the late 1980s in the U.K. The main aim is to examine what has happened to the rela.LluH.51úp ~o::;~w=1L ul~uuisation anel }Jfolltauiiüy after the changes in the union legislation, competition environrnent and cyclical variations that took place over this period. The impact of different forms of union-firm bargaining on the union-profitability effect is also examined. The data reveal that the negative union effect on profitability exists, even after controlling for firm specific fixed effects, that it is larger where unions negotiate jointly with the firm as part of industry leveI bargaining, but that it has been sharply reduced over the 1980s.

Governos eficientes e serviços públicos efetivos: contribuições a partir da Teoria do Valor Público

O presente artigo discute as necessidades de aprimoramento na eficiência gerencial dos governos, a partir de inovações na elaboração e provisão dos serviços públicos. Alerta, porém, que não há muitas vantagens em ser eficiente em serviços que não geram valor para a população. Por esta razão, o texto procura associar estes dois vetores sobre o alicerce conceitual da teoria do valor público, a qual vai além da discussão da eficiência no desempenho governamental para resultados, e discorre sobre a geração de impacto na atuação do poder público, em termos do que seria seu propósito estratégico. Norteado por este viés metodológico, o artigo tratará sobre os aspectos de priorização, financiamento e aprimoramento de serviços públicos, como alternativas para fomentar a estruturação de governos eficientes na gestão e efetivos nos impactos que visam produzir.

Otimização e análise mecânica de pastas geopoliméricas para uso em poços sujeitos à injeção cíclica de vapor

Oil wells subjected to cyclic steam injection present important challenges for the development of well cementing systems, mainly due to tensile stresses caused by thermal gradients during its useful life. Cement sheath failures in wells using conventional high compressive strength systems lead to the use of cement systems that are more flexible and/or ductile, with emphasis on Portland cement systems with latex addition. Recent research efforts have presented geopolymeric systems as alternatives. These cementing systems are based on alkaline activation of amorphous aluminosilicates such as metakaolin or fly ash and display advantageous properties such as high compressive strength, fast setting and thermal stability. Basic geopolymeric formulations can be found in the literature, which meet basic oil industry specifications such as rheology, compressive strength and thickening time. In this work, new geopolymeric formulations were developed, based on metakaolin, potassium silicate, potassium hydroxide, silica fume and mineral fiber, using the state of the art in chemical composition, mixture modeling and additivation to optimize the most relevant properties for oil well cementing. Starting from molar ratios considered ideal in the literature (SiO2/Al2O3 = 3.8 e K2O/Al2O3 = 1.0), a study of dry mixtures was performed,based on the compressive packing model, resulting in an optimal volume of 6% for the added solid material. This material (silica fume and mineral fiber) works both as an additional silica source (in the case of silica fume) and as mechanical reinforcement, especially in the case of mineral fiber, which incremented the tensile strength. The first triaxial mechanical study of this class of materials was performed. For comparison, a mechanical study of conventional latex-based cementing systems was also carried out. Regardless of differences in the failure mode (brittle for geopolymers, ductile for latex-based systems), the superior uniaxial compressive strength (37 MPa for the geopolymeric slurry P5 versus 18 MPa for the conventional slurry P2), similar triaxial behavior (friction angle 21° for P5 and P2) and lower stifness (in the elastic region 5.1 GPa for P5 versus 6.8 GPa for P2) of the geopolymeric systems allowed them to withstand a similar amount of mechanical energy (155 kJ/m3 for P5 versus 208 kJ/m3 for P2), noting that geopolymers work in the elastic regime, without the microcracking present in the case of latex-based systems. Therefore, the geopolymers studied on this work must be designed for application in the elastic region to avoid brittle failure. Finally, the tensile strength of geopolymers is originally poor (1.3 MPa for the geopolymeric slurry P3) due to its brittle structure. However, after additivation with mineral fiber, the tensile strength became equivalent to that of latex-based systems (2.3 MPa for P5 and 2.1 MPa for P2). The technical viability of conventional and proposed formulations was evaluated for the whole well life, including stresses due to cyclic steam injection. This analysis was performed using finite element-based simulation software. It was verified that conventional slurries are viable up to 204ºF (400ºC) and geopolymeric slurries are viable above 500ºF (260ºC)

Efeitos de peixes zooplanctívoros e onívoros sobre a resposta de comunidades planctônicas à fertilização por nutrientes

The food chain theory predict that presence of omnivory prevent the trophic cascade and could be a strong stabilizing factor over resource and consumer community dynamics, and that the nutrient enrichment destabilize populations dynamics. Most of the freshwater tropical reservoirs are eutrophic, and strategies that seek improve the water quality through the control of phytoplankton biomass and nutrient input, become essential for the improvement and preservation of water quality. The aim of this study was test the zooplanktivory (when larvae) and omnivory (when young and adult) effects of Nile Tilapia over the structure and dynamics of plankton communities, in addition or absence of nutrients enrichment. For this, one field experiment was performed with a factorial design 2x3 resulting in six treatments: control, without fish and nutrient (C); with omnivorous fish (O); with zooplanktivorous fish (Z); without fish and with enrichment of nutrients (NP); with omnivorous fish and nutrients (ONP); and, with zooplanktivorous fish and nutrients (ZNP). The two planktivory types reduced the zooplankton biomass and increased the phytoplankton biomass, but the omnivory of filter-feeding fish attenuated the trophic cascade magnitude. The fertilization by nutrients increases the nutrient concentrations in water and the phytoplankton biomass, but the effect on zooplankton is dependent of the trophic structure. In a general way, the effects of the fish and nutrient addition were addictive, but significant interactions among those factors were observed in the answer of some zooplankton groups. The effects of omnivorous fish over the temporal variability of phytoplankton and zooplankton biomass were very variable, the increase or reduce in variability of the plankton depending of the level of nutrients and of the analyzed variable. With base in this study, we conclude that the planktivory type exercised by the fish and the concentrations of nutrients in the water affects the force of pelagic trophic cascades and probably the success of biomanipulation programs for the handling of water quality in lakes and tropical reservoirs

Segurança das condições de aplicação de herbicidas com aerobarco em plantas daninhas aquáticas no lago da Hidrelétrica de Jupiá

Os objetivos deste trabalho foram quantificar as exposições dérmicas (EDs) e respiratórias (ERs) proporcionadas ao piloto e ao seu ajudante nas aplicações de herbicidas para o controle de plantas daninhas aquáticas com aerobarco; classificar essas condições de trabalho em seguras ou inseguras; e calcular a necessidade de controle das exposições (NCE) e o tempo de trabalho seguro (TTS). O aerobarco utilizado tinha casco de alumínio (4,85 x 2,42 m) e acionamento por hélice acoplada a motor a gasolina de 350 HP. O equipamento de pulverização era composto por bomba de diafragma com fluxo máximo de 49,69 L min-1, pressão máxima de 25 kg cm-2, acionada por motor a gasolina de 4 HP, e tanque de calda de 189 L. A barra de pulverização de alumínio era composta de duas seções laterais de 3 m, posicionadas na linha entre o encosto do banco do piloto e o início da estrutura protetora da hélice. Cada seção da barra tinha seis bicos com pontas de jato plano com indução de ar AI 100 03, espaçados de 0,5 m, e uma ponta OC 20 fixada em cada extremidade. O conjunto de pontas pulverizava faixas de 6 m de largura e aplicava o volume de calda de 200 L ha-1. O sistema tinha gerenciador de fluxo, controlado por central eletrônica acoplada a DGPS (com precisão submétrica), para corrigir automaticamente a vazão em função de alterações na velocidade real da embarcação. As EDs e ERs aos herbicidas foram calculadas com os dados substitutos das exposições às caldas, avaliadas com os traçadores cobre e manganês adicionados às caldas. As exposições foram extrapoladas para uma jornada de trabalho de seis horas. A segurança das condições de trabalho foi determinada com o cálculo da margem de segurança (MS), utilizando-se a fórmula MS = (NOEL x 70)/(QAE x 10), em que QAE = quantidade absorvível da exposição. As condições de trabalho foram classificadas em seguras, se MS>1, ou inseguras, se MS<1. As exposições proporcionadas pelas condições de trabalho foram de 10,65 mL de calda por dia para o piloto e de 16,80 mL por dia para o ajudante, que fica sentado em uma cadeira a 2,0 m à frente do piloto e da barra de pulverização. Classificaram-se como seguras as aplicações dos herbicidas glyphosate (Rodeo, 6 L ha-1), 2,4D (DMA 806 BR, 8 L ha-1) e fluridone (Sonar AQ, 0,4 L ha-1), para o piloto e o seu ajudante. Classificou-se como insegura a aplicação do herbicida diquat (Reward, 4,0 L ha-1) para as duas condições de trabalho, cujas necessidades de controle das exposições calculadas foram de 65% para o piloto e de 78% para o ajudante do piloto.