Investigation and optimization of parameters affecting the multiply charged ion yield in AP-MALDI MS

Liquid matrix-assisted laser desorption/ionization (MALDI) allows the generation of predominantly multiply charged ions in atmospheric pressure (AP) MALDI ion sources for mass spectrometry (MS) analysis. The charge state distribution of the generated ions and the efficiency of the ion source in generating such ions crucially depend on the desolvation regime of the MALDI plume after desorption in the AP-tovacuum inlet. Both high temperature and a flow regime with increased residence time of the desorbed plume in the desolvation region promote the generation of multiply charged ions. Without such measures the application of an electric ion extraction field significantly increases the ion signal intensity of singly charged species while the detection of multiply charged species is less dependent on the extraction field. In general, optimization of high temperature application facilitates the predominant formation and detection of multiply charged compared to singly charged ion species. In this study an experimental setup and optimization strategy is described for liquid AP-MALDI MS which improves the ionization effi- ciency of selected ion species up to 14 times. In combination with ion mobility separation, the method allows the detection of multiply charged peptide and protein ions for analyte solution concentrations as low as 2 fmol/lL (0.5 lL, i.e. 1 fmol, deposited on the target) with very low sample consumption in the low nL-range.

Stochastic simulations of the Madden-Julian oscillation activity

The Madden-Julian oscillation (MJO) is the most prominent form of tropical intraseasonal variability. This study investigated the following questions. Do inter-annual-to-decadal variations in tropical sea surface temperature (SST) lead to substantial changes in MJO activity? Was there a change in the MJO in the 1970s? Can this change be associated to SST anomalies? What was the level of MJO activity in the pre-reanalysis era? These questions were investigated with a stochastic model of the MJO. Reanalysis data (1948-2008) were used to develop a nine-state first order Markov model capable to simulate the non-stationarity of the MJO. The model is driven by observed SST anomalies and a large ensemble of simulations was performed to infer the activity of the MJO in the instrumental period (1880-2008). The model is capable to reproduce the activity of the MJO during the reanalysis period. The simulations indicate that the MJO exhibited a regime of near normal activity in 1948-1972 (3.4 events year(-1)) and two regimes of high activity in 1973-1989 (3.9 events) and 1990-2008 (4.6 events). Stochastic simulations indicate decadal shifts with near normal levels in 1880-1895 (3.4 events), low activity in 1896 1917 (2.6 events) and a return to near normal levels during 1918-1947 (3.3 events). The results also point out to significant decadal changes in probabilities of very active years (5 or more MJO events): 0.214 (1880-1895), 0.076 (1896-1917), 0.197 (1918-1947) and 0.193 (1948-1972). After a change in behavior in the 1970s, this probability has increased to 0.329 (1973-1989) and 0.510 (1990-2008). The observational and stochastic simulations presented here call attention to the need to further understand the variability of the MJO on a wide range of time scales.

Dynamics of two planets in co-orbital motion

We study the stability regions and families of periodic orbits of two planets locked in a co-orbital configuration. We consider different ratios of planetary masses and orbital eccentricities; we also assume that both planets share the same orbital plane. Initially, we perform numerical simulations over a grid of osculating initial conditions to map the regions of stable/chaotic motion and identify equilibrium solutions. These results are later analysed in more detail using a semi-analytical model. Apart from the well-known quasi-satellite orbits and the classical equilibrium Lagrangian points L(4) and L(5), we also find a new regime of asymmetric periodic solutions. For low eccentricities these are located at (delta lambda, delta pi) = (+/- 60 degrees, -/+ 120 degrees), where delta lambda is the difference in mean longitudes and delta pi is the difference in longitudes of pericentre. The position of these anti-Lagrangian solutions changes with the mass ratio and the orbital eccentricities and are found for eccentricities as high as similar to 0.7. Finally, we also applied a slow mass variation to one of the planets and analysed its effect on an initially asymmetric periodic orbit. We found that the resonant solution is preserved as long as the mass variation is adiabatic, with practically no change in the equilibrium values of the angles.

Rainforest Aerosols as Biogenic Nuclei of Clouds and Precipitation in the Amazon

The Amazon is one of the few continental regions where atmospheric aerosol particles and their effects on climate are not dominated by anthropogenic sources. During the wet season, the ambient conditions approach those of the pristine pre-industrial era. We show that the fine submicrometer particles accounting for most cloud condensation nuclei are predominantly composed of secondary organic material formed by oxidation of gaseous biogenic precursors. Supermicrometer particles, which are relevant as ice nuclei, consist mostly of primary biological material directly released from rainforest biota. The Amazon Basin appears to be a biogeochemical reactor, in which the biosphere and atmospheric photochemistry produce nuclei for clouds and precipitation sustaining the hydrological cycle. The prevailing regime of aerosol-cloud interactions in this natural environment is distinctly different from polluted regions.

Polarization and Spectral Shift of Benzophenone in Supercritical Water

Monte Carlo simulation and quantum mechanics calculations based on the INDO/CIS and TD-DFT methods were utilized to study the solvatochromic shift of benzophenone when changing the environment from normal water to supercritical (P = 340.2 atm and T = 673 K) condition. Solute polarization increases the dipole moment of benzophenone, compared to gas phase, by 88 and 35% in normal and supercritical conditions, giving the in-solvent dipole value of 5.8 and 4.2 D, respectively. The average number of solute-solvent hydrogen bonds was analyzed, and a large decrease of 2.3 in normal water to only 0.8 in the supercritical environment was found. By using these polarized models of benzophenone in the two different conditions of water, we performed MC simulations to generate statistically uncorrelated configurations of the solute surrounded by the solvent molecules and subsequent quantum mechanics calculations on these configurations. When changing from normal to supercritical water environment, INDO/CIS calculations explicitly considering all valence electrons of the 235 solvent water molecules resulted in a solvatochromic shift of 1425 cm(-1) for the most intense transition of benzophenone, that is, slightly underestimated in comparison with the experimentally inferred result of 1700 cm(-1). TD-B3LYP/6-311+G(2d,p) calculations on the same configurations but with benzophenone electrostatically embedded in the 320 water molecules resulted in a solvatochromic shift of 1715 cm(-1) for this transition, in very good agreement with the experimental result. When using the unpolarized model of the benzophenone, this calculated solvatochromic shift was only 640 cm(-1). Additional calculations were also made by using BHandHLYP/6-311+G(2d,p) to analyze the effect of the asymptotic decay of the exchange functional. This study indicates that, contrary to the general expectation, there is a sizable solute polarization even in the low-density regime of supercritical condition and that the inclusion of this polarization is important for a reliable description of the spectral shifts considered here.

Action of the gravitational field on the dynamical Casimir effect

In this paper, we analyze the action of the gravitational field on the dynamical Casimir effect. We consider a massless scalar field confined in a cuboid cavity placed in a gravitational field described by a static and diagonal metric. With one of the plane mirrors of the cavity allowed to move, we compute the average number of particles created inside the cavity by means of the Bogoliubov coefficients computed through perturbative expansions. We apply our result to the case of an oscillatory motion of the mirror, assuming a weak gravitational field described by the Schwarzschild metric. The regime of parametric amplification is analyzed in detail, demonstrating that our computed result for the mean number of particles created agrees with specific associated cases in the literature. Our results, obtained in the framework of the perturbation theory, are restricted, under resonant conditions, to a short-time limit.

Lifestyle and health status in a sample of Swedish women four years after pregnancy : a comparison of women with a history of normal pregnancy and women with a history of gestational diabetes mellitus

Background: Despite the recommendations to continue the regime of healthy food and physical activity (PA) postpartum for women with previous gestational diabetes mellitus (GDM), the scientific evidence reveals that these recommendations may not be complied to. This study compared lifestyle and health status in women whose pregnancy was complicated by GDM with women who had a normal pregnancy and delivery. Methods: The inclusion criteria were women with GDM (ICD-10: O24.4 A and O24.4B) and women with uncomplicated pregnancy and delivery in 2005 (ICD-10: O80.0). A random sample of women fulfilling the criteria (n = 882) were identified from the Swedish Medical Birth Register. A questionnaire was sent by mail to eligible women approximately four years after the pregnancy. A total of 444 women (50.8%) agreed to participate, 111 diagnosed with GDM in their pregnancy and 333 with normal pregnancy/ delivery. Results: Women with previous GDM were significantly older, reported higher body weight and less PA before the index pregnancy. No major differences between the groups were noticed regarding lifestyle at the follow-up. Overall, few participants fulfilled the national recommendations of PA and diet. At the follow-up, 19 participants had developed diabetes, all with previous GDM. Women with previous GDM reported significantly poorer self-rated health (SRH), higher level of sick-leave and more often using medication on regular basis. However, a history of GDM or having overt diabetes mellitus showed no association with poorer SRH in the multivariate analysis. Irregular eating habits, no regular PA, overweight/obesity, and regular use of medication were associated with poorer SRH in all participants. Conclusions: Suboptimal levels of PA, and fruit and vegetable consumption were found in a sample of women with a history of GDM as well as for women with normal pregnancy approximately four years after index pregnancy. Women with previous GDM seem to increase their PA after childbirth, but still they perform their PA at lower intensity than women with a history of normal pregnancy. Having GDM at index pregnancy or being diagnosed with overt diabetes mellitus at follow-up did not demonstrate associations with poorer SRH four years after delivery.

Overdetermination in a marxian theory of money

O presente artigo focaliza a genérica e abstrata análise monetária desenvolvida por Marx no inicio do Capital. Mais precisamente, pretende-se avaliar em que medida, se alguma, alguns aspectos da análise de Marx sobre o papel bastante contraditório desempenhado pela moeda no processo de circulação simples de mercadorias suportam uma interpretação sobre-determinista do método dialético por ele empregado. Baseando-se no conceito de sobre-determinação introduzido na literature Marxiana principalmente por Louis Althusser, o artigo conclui que o nexo real-monetário prevalecente na circulação simples de mercadorias pode ser concebida como um nexo sobre-determinado, ou seja, um nexo caracterizado por incorporar um regime de constitutividade.

Implementação de um regime centralizador de matrícula por disciplina numa instituição particular de ensino superior

O objetivo do estudo foi analisar a implementação de um Regime Centralizador de Matrícula por Disciplina nas Faculdades Integradas Simonsen. Buscou-se, através do Regime Centralizador,eliminar as dificuldades inerentes ã aplicação, em Instituições de Ensino Superior brasileiras, do Regime de Matrículas por Disciplina alienígena.

Venda de ativos operacionais e assimetria de informação: estudo comparativo entre o regime jurídico do contrato de trespasse e da recuperação judicial

Primeiramente, o presente trabalho se presta a demonstrar a relevância da recuperação judicial de empresas no que diz respeito à maximização de valor dos bens, considerados em conjunto (valor de going concern), quando mantidos operacionais, conforme teoria do common pool assets. Posteriormente, será verificado como deve ser a estruturação do regime legal da venda de ativos de forma a maximizar valor dos bens alienados, juntamente com uma comparação entre os regimes jurídicos do contrato de trespasse, regulado pelo Código Civil de 2002, e da recuperação judicial, estabelecido na Lei 11.101/05, especificamente no que diz respeito à venda de unidades produtivas isoladas. A diferenciação dos institutos do trespasse e da recuperação judicial será feita principalmente com base em características relacionadas à sucessão do passivo do estabelecimento comercial (ou unidade produtiva) no momento de sua alienação a terceiros, e como a assimetria de informação pode influenciar na maximização do valor, no momento da venda dos bens, em cada um dos regimes.

Macroeconomic constraints to growth of Brazilian economy diagnosis and some policy proposals

The recent process of accelerated expansion of the Brazilian economy was driven by exports and fixed capital formation. Although the pace of growth was more robust than in the 1990´s, we can still witness the existence of certain macroeconomic constraints to its continuation in the long run such as, for instance, the exchange rate overvaluation in particular since 2005, and in general the modus operandi of monetary policy. Such constraints may jeopardize the sustainability of the current pace of growth. Therefore, we argue that Brazil still lies in a trap made up of high interest and low exchange rates. The elimination of the exchange rate misalignment would bring about a great increase in the rate of interest, which on its turn would impact negatively upon investment and hence upon the sustainability of long run economic growth. We outline a set of policy measures to eliminate such a trap, in particular, the adoption of an implicit target for the exchange rate, capital controls and the abandonment of the present regime of inflation targeting. Recent events seem to go in this direction.

Caracterização analítica e geométrica da metodologia geral de determinação de distribuições de Weibull para o regime eólico e suas aplicações

O regime eólico de uma região pode ser descrito por distribuição de frequências que fornecem informações e características extremamente necessárias para uma possível implantação de sistemas eólicos de captação de energia na região e consequentes aplicações no meio rural em regiões afastadas. Estas características, tais como a velocidade média anual, a variância das velocidades registradas e a densidade da potência eólica média horária, podem ser obtidas pela frequência de ocorrências de determinada velocidade, que por sua vez deve ser estudada através de expressões analíticas. A função analítica mais adequada para distribuições eólicas é a função de densidade de Weibull, que pode ser determinada por métodos numéricos e regressões lineares. O objetivo deste trabalho é caracterizar analítica e geometricamente todos os procedimentos metodológicos necessários para a realização de uma caracterização completa do regime eólico de uma região e suas aplicações na região de Botucatu - SP, visando a determinar o potencial energético para implementação de turbinas eólicas. Assim, foi possível estabelecer teoremas relacionados com a forma de caracterização do regime eólico, estabelecendo a metodologia concisa analiticamente para a definição dos parâmetros eólicos de qualquer região a ser estudada. Para o desenvolvimento desta pesquisa, utilizou-se um anemômetro da CAMPBELL.

A influência da poluição difusa e do regime hidrológico peculiar do semiárido na qualidade da água de um reservatório tropical

In semiarid region of northeast Brazil, the majority of reservoirs used for public supply has suffered degradation of water quality affected by diffuse pollution from agricultural and livestock areas of the watershed and by hydrologic regime peculiar to the region, characterized by a rainy season with higher volumes stored in reservoirs and a dry season with a reduction in water level due to high evaporation and increase of eutrophication. The Dourado reservoir, located in Currais Novos city, semiarid region of Rio Grande do Norte state, is one example of a water supply reservoir that can have degradation of water quality and impracticability of their use, due to the high external input of nutrients from non-point sources of watershed during the rainy season and increasing of eutrophication due to decrease the stored volume during the dry period. This study aimed to investigate and quantify diffuse pollution and the hydrologic regime of semiarid region in order to establish standards regarding the water quality of Dourado reservoir. The study period was between the months of May 2011 to March 2012. The diffuse pollution was quantified in terms of watershed from the mass balance of phosphorus in the reservoir, as in relation to areas under different types of land use within the riparian zone of the reservoir from the assessment of soil chemical properties and losses of phosphorus in each area. The influence of hydrological regime on water quality of the reservoir was evaluated from the monthly monitoring of the morphometric, meteorological and limnological features throughout the study period. The results showed that the reservoir has received a high load of phosphorus coming from the drainage basin and presents itself as a system able to retain some of that load tributary, giving an upward trend of the eutrophication process. Diffuse pollution by nutrients from areas under different types of land use within the riparian zone of the reservoir was higher in areas under the influence of livestock, being this area considered a potential diffuse source of nutrients to the reservoir. Regarding the water regime during the rainy season the reservoir was characterized by high concentrations of nutrients and small algal biomass, while in the dry season the reduction of volume and increase of the water retention time of the reservoir, contributing to the excessive growth algal biomass, favoring an increase in eutrophication and deterioration of water quality. In synthesis the water quality of Dourado reservoir is directed by diffuse pollution coming from the drainage basin and the hydrological regime of the peculiar semiarid region, where the rainy season is characterized by high input of allochthonous compounds from the tributaries and erosion of the soil in the reservoir riparian zone, and the dry season characterized by reducing the storage volume due to high evaporation, high residence time of water and consequent degradation of water quality due to the increase of eutrophication process

O efeito do regime hidrológico do semiárido na composição de espécies durante dominância de cianobactérias em um reservatório tropical

The potentially toxic cyanobacterial blooms in water bodies are spread across the globe, resulting in the loss of water quality and adverse effects on human health. In arid and semiarid regions, the hydrologic regime characterized by an annual cycle of drought and rain, change the volume and the retention time of the reservoir. Such changes affect the limnological characteristics and causing changes in composition and biomass community of cyanobacteria. The reservoir Cruzeta (Zmax = 8.7 m) is a eutrophic water supply source located in the semiarid tropical (Northeast Brazil). Raised the hypothesis that the hydrological regime of semi-arid tropical is a determining factor in the availability of resources in eutrophic water sources, which influences the composition of dominant species of cyanobacteria. The aim of this study was to analyze the changes in biomass and species composition of cyanobacteria for two annual hydrological cycles and evaluate factors drivers. The study was divided into five distinct periods (dry 2010, rain 2011, dry 2011, rain 2012, dry 2012). The dominant group found in all periods was Cyanobacteria (99% of total biomass), which contributed to the low diversity. The filamentous species Cylindrospermopsis raciborskii was present at both points in almost every study. The colonial species Microcystis panniformis and Sphaerocavum brasiliensis dominated only in periods with lower volumes of water. The diatoms contribute more to the biomass during the period of severe drought. The point near the dam (P1) had phytoplankton biomass larger than the point near the tributary (P2). The dominant species of colonial cyanobacteria lasted until the overflow in P1, and P2 this dominance was until the first rains. The redundancy analysis indicated that physical factors such as light availability and water level were the main factors driving the seasonal succession of phytoplankton. The composition of phytoplankton in spring was alternated by species of filamentous cyanobacteria in conditions of poor stability of the water column, such as Cylindrospermopsis raciborskii, and colonial species under conditions of high stability of the water column, such as Microcystis panniformis and Sphaerocavum brasiliensis. The extremes of torrential rains and severe droughts, governed by the hydrological regime of the semi-arid region led to the availability of resources in the watershed, directing the spatial and temporal dynamics of phytoplankton in the reservoir Cruzeta

Renormalizability of generalized quantum electrodynamics

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)