A three-state model for the photophysics of guanine

The nonadiabatic photochemistry of the guanine molecule (2-amino-6-oxopurine) and some of its tautomers has been studied by means of the high-level theoretical ab initio quantum chemistry methods CASSCF and CASPT2. Accurate computations, based by the first time on minimum energy reaction paths, states minima, transition states, reaction barriers, and conical intersections on the potential energy hypersurfaces of the molecules lead to interpret the photochemistry of guanine and derivatives within a three-state model. As in the other purine DNA nucleobase, adenine, the ultrafast subpicosecond fluorescence decay measured in guanine is attributed to the barrierless character of the path leading from the initially populated (1)(pi pi* L-a) spectroscopic state of the molecule toward the low-lying methanamine-like conical intersection (gs/pi pi* L-a)(CI). On the contrary, other tautomers are shown to have a reaction energy barrier along the main relaxation profile. A second, slower decay is attributed to a path involving switches toward two other states, (1)(pi pi* L-b) and, in particular, (1)(n(o)pi*), ultimately leading to conical intersections with the ground state. A common framework for the ultrafast relaxation of the natural nucleobases is obtained in which the predominant role of a pi pi*-type state is confirmed.

Three essays on local demand for public services

Local provision of public services has the positive effect of increasing the efficiency because each locality has its idiosyncrasies that determine a particular demand for public services. This dissertation addresses different aspects of the local demand for public goods and services and their relationship with political incentives. The text is divided in three essays. The first essay aims to test the existence of yardstick competition in education spending using panel data from Brazilian municipalities. The essay estimates two-regime spatial Durbin models with time and spatial fixed effects using maximum likelihood, where the regimes represent different electoral and educational accountability institutional settings. First, it is investigated whether the lame duck incumbents tend to engage in less strategic interaction as a result of the impossibility of reelection, which lowers the incentives for them to signal their type (good or bad) to the voters by mimicking their neighbors’ expenditures. Additionally, it is evaluated whether the lack of electorate support faced by the minority governments causes the incumbents to mimic the neighbors’ spending to a greater extent to increase their odds of reelection. Next, the essay estimates the effects of the institutional change introduced by the disclosure on April 2007 of the Basic Education Development Index (known as IDEB) and its goals on the strategic interaction at the municipality level. This institutional change potentially increased the incentives for incumbents to follow the national best practices in an attempt to signal their type to voters, thus reducing the importance of local information spillover. The same model is also tested using school inputs that are believed to improve students’ performance in place of education spending. The results show evidence for yardstick competition in education spending. Spatial auto-correlation is lower among the lame ducks and higher among the incumbents with minority support (a smaller vote margin). In addition, the institutional change introduced by the IDEB reduced the spatial interaction in education spending and input-setting, thus diminishing the importance of local information spillover. The second essay investigates the role played by the geographic distance between the poor and non-poor in the local demand for income redistribution. In particular, the study provides an empirical test of the geographically limited altruism model proposed in Pauly (1973), incorporating the possibility of participation costs associated with the provision of transfers (Van de Wale, 1998). First, the discussion is motivated by allowing for an “iceberg cost” of participation in the programs for the poor individuals in Pauly’s original model. Next, using data from the 2000 Brazilian Census and a panel of municipalities based on the National Household Sample Survey (PNAD) from 2001 to 2007, all the distance-related explanatory variables indicate that an increased proximity between poor and non-poor is associated with better targeting of the programs (demand for redistribution). For instance, a 1-hour increase in the time spent commuting by the poor reduces the targeting by 3.158 percentage points. This result is similar to that of Ashworth, Heyndels and Smolders (2002) but is definitely not due to the program leakages. To empirically disentangle participation costs and spatially restricted altruism effects, an additional test is conducted using unique panel data based on the 2004 and 2006 PNAD, which assess the number of benefits and the average benefit value received by beneficiaries. The estimates suggest that both cost and altruism play important roles in targeting determination in Brazil, and thus, in the determination of the demand for redistribution. Lastly, the results indicate that ‘size matters’; i.e., the budget for redistribution has a positive impact on targeting. The third essay aims to empirically test the validity of the median voter model for the Brazilian case. Information on municipalities are obtained from the Population Census and the Brazilian Supreme Electoral Court for the year 2000. First, the median voter demand for local public services is estimated. The bundles of services offered by reelection candidates are identified as the expenditures realized during incumbents’ first term in office. The assumption of perfect information of candidates concerning the median demand is relaxed and a weaker hypothesis, of rational expectation, is imposed. Thus, incumbents make mistakes about the median demand that are referred to as misperception errors. Thus, at a given point in time, incumbents can provide a bundle (given by the amount of expenditures per capita) that differs from median voter’s demand for public services by a multiplicative error term, which is included in the residuals of the demand equation. Next, it is estimated the impact of the module of this misperception error on the electoral performance of incumbents using a selection models. The result suggests that the median voter model is valid for the case of Brazilian municipalities.

Three applications of the marginal cost of public funds concept

This paper illustrates the use of the marginal cost of public funds concept in three contexts. First, we extend Parry’s (2003) analysis of the efficiency effects excise taxes in the U.K., primarily by incorporating the distortion caused by imperfect competition in the cigarette market and distinguishing between the MCFs for per unit and ad valorem taxes on cigarettes. Our computations show, contrary to the standard result in the literature, that the per unit tax on cigarettes has a slightly lower MCF than the ad valorem tax on cigarettes. Second, we calculate the MCF for a payroll tax in a labour market with involuntary unemployment, using the Shapiro and Stiglitz (1984) efficiency wage model as our framework. Our computations, based on Canadian labour market data, indicate that incorporating the distortion caused by involuntary unemployment raises the MCF by 25 to 50 percent. Third, we derive expressions for the distributionally-weighted MCFs for the exemption level and the marginal tax rate for a “flat tax”, such as the one that has been adopted by the province of Alberta. This allows us to develop a restricted, but tractable, version of the optimal income tax problem. Computations indicate that the optimal marginal tax rate may be quite high, even with relatively modest pro-poor distributional preferences.

The impact of the 2008 economic recession on three residential property type investments: a case study of five diverse zip codes in Washington DC, USA

There has been 47 recessions in the United States of America (US) since 1790. US recessions have increasingly affected economies of other countries in the world as nations become more and more interdependent on each other. The worst economic recession so far was the “Great Depression” – an economic recession that was caused by the 1929 crash of the stock market in the US. The 2008 economic recession in the US was a result of the burst of the “housing bubble” created by predatory lending. The economic recession resulted in increased unemployment (according to NBER 8.7 million jobs were lost from Feb. 2008 to Feb. 2010); decrease in GDP by 5.1%; increase in poverty level from 12.1% (2007) to 16.0% (2008) (NBER) This dissertation is an attempt to research the impact of the 2008 economic recession on different types of residential investments: a case study of five (5) diverse neighborhoods/zip codes in Washington DC, USA The main findings were that the effect of the 2008 economic depression on the different types of residential properties was dependent on the location of the property and the demographics/socio-economic factors associated with that location.

Coordenação e governança no Programa Territórios da Cidadania: uma análise multi-level a partir do Vale do Ribeira-SP

Poverty in Brazil has been gradually reduced. Among the main reasons, there are public policies for universalization of rights. On the other hand, the municipalities' Human Development Index indicates scenarios of growing inequality. In other words, some regions, basically of rural character, were left behind in that process of development. In 2008, the “Territórios da Cidadania” (Territories of Citizenship) Program was launched by the federal government, under high expectations. It was proposed to develop those regions and to prioritize the arrival of ongoing federal public policies where they were most demanded. The program has shown an innovative arrangement which included dozens of ministries and other federal agencies, state governments, municipalities and collegialities to the palliative management and control of the territory. In this structure, both new and existing jurisdictions came to support the program coordination. This arrangement was classified as an example of multi-level governance, whose theory has been an efficient instrument to understand the intra- and intergovernmental relations under which the program took place. The program lasted only three years. In Vale do Ribeira Territory – SP, few community leaderships acknowledge it, although not having further information about its actions and effects. Against this background, the approach of this research aims to study the program coordination and governance structure (from Vale Territory, considered as the most local level, until the federal government), based on the hypothesis that, beyond the local contingencies in Vale do Ribeira, the layout and implementation of the Territories of Citizenship Program as they were formulated possess fundamental structural issues that hinder its goals of reducing poverty and inequality through promoting the development of the territory. Complementing the research, its specific goal was to raise the program layout and background in order to understand how the relations, predicted or not in its structure, were formulated and how they were developed, with special attention to Vale do Ribeira-SP. Generally speaking, it was concluded that the coordination and governance arrangement of the Territories of Citizenship Program failed for not having developed qualified solutions to deal with the challenges of the federalist Brazilian structure, party politics, sectorized public actions, or even the territory contingencies and specificities. The complexity of the program, the poverty problem proposed to be faced, and the territorial strategy of development charged a high cost of coordination, which was not accomplished by the proposal of centralization in the federal government with internal decentralization of the coordination. As the presidency changed in 2011, the program could not present results that were able to justify the arguments for its continuation, therefore it was paralyzed, lost its priority status, and the resources previously invested were redirected.

Estudo e desenvolvimento de um capacitor eletrolítico de nióbio

It seeks to find an alternative to the current tantalum electrolytic capacitors in the market due to its high cost. Niobium is a potential substitute, since both belong to the same group of the periodic table and because of this have many similar physical and chemical properties. Niobium has several technologically important applications, and Brazil has the largest reserves, around 96%. There are including niobium in reserves of tantalite and columbite in Rio Grande do Norte. These electrolytic capacitors have high capacitance specifies, ie they can store high energy in small volumes compared to other types of capacitors. This is the main attraction of this type of capacitor because is growing demand in the production of capacitors with capacitance specifies increasingly high, this because of the miniaturization of various devices such as GPS devices, televisions, computers, phones and many others. The production route of the capacitor was made by powder metallurgy. The initial niobium powder supplied by EEL-USP was first characterized by XRD, SEM, XRF and laser particle size, to then be sieved into three particle size, 200, 400 e 635mesh. The powders were then compacted and sintered at 1350, 1450 and 1550°C using two sintering time 30 and 60min. Sintering is one of the most important parts of the process as it affects properties as porosity and surface cleaning of the samples, which greatly affected the quality of the capacitor. The sintered samples then underwent a process of anodic oxidation, which created a thin film of niobium pentóxido over the whole porous surface of the sample, this film is the dielectric capacitor. The oxidation process variables influence the performance of the film and therefore the capacitor. The samples were characterized by electrical measurements of capacitance, loss factor, ESR, relative density, porosity and surface area. After the characterizations was made an annealing in air ate 260ºC for 60min. After this treatment were made again the electrical measurements. The particle size of powders and sintering affected the porosity and in turn the specific area of the samples. The larger de area of the capacitor, greater is the capacitance. The powder showed the highest capacitance was with the smallest particle size. Higher temperatures and times of sintering caused samples with smaller surface area, but on the other hand the cleaning surface impurities was higher for this cases. So a balance must be made between the gain that is achieved with the cleaning of impurities and the loss with the decreased in specific area. The best results were obtained for the temperature of 1450ºC/60min. The influence of annealing on the loss factor and ESR did not follow a well-defined pattern, because their values increased in some cases and decreased in others. The most interesting results due to heat treatment were with respect to capacitance, which showed an increase for all samples after treatment

Feeding level and frequency for freshwater angelfish

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Uma fonte chaveada de 50kW com correção de fator de potência para alimentação de uma tocha de plasma Indutiva utilizando técnicas de controle digital

This work deals with the development of an experimental study on a power supply of high frequency that provides the toch plasmica to be implemented in PLASPETRO project, which consists of two static converters developed by using Insulated Gate Bipolar Transistor (IGBT). The drivers used to control these keys are triggered by Digital Signal Processor (DSP) through optical fibers to reduce problems with electromagnetic interference (EMI). The first stage consists of a pre-regulator in the form of an AC to DC converter with three-phase boost power factor correction which is the main theme of this work, while the second is the source of high frequency itself. A series-resonant inverter consists of four (4) cell inverters operating in a frequency around 115 kHz each one in soft switching mode, alternating itself to supply the load (plasma torch) an alternating current with a frequency of 450 kHz. The first stage has the function of providing the series-resonant inverter a DC voltage, with the value controlled from the power supply provided by the electrical system of the utility, and correct the power factor of the system as a whole. This level of DC bus voltage at the output of the first stage will be used to control the power transferred by the inverter to the load, and it may vary from 550 VDC to a maximum of 800 VDC. To control the voltage level of DC bus driver used a proportional integral (PI) controller and to achieve the unity power factor it was used two other proportional integral currents controllers. Computational simulations were performed to assist in sizing and forecasting performance. All the control and communications needed to stage supervisory were implemented on a DSP

Ultrastructural analysis of the low level laser therapy effects on the lesioned anterior tibial muscle in the Gerbil

Low level laser therapy (LLLT) is known for its positive results but studies on the biological and biomodulator characteristics of the effects produced in the skeletal muscle are Still lacking. In this Study the effects of two laser dosages, 5 or 10 J/cm(2), on the lesioned tibial muscle were compared. Gerbils previously lesioned by 100 g load impact were divided into three groups: GI (n = 5) controls, lesion non-irradiated; GII (n = 5), lesion irradiated with 5 J/Cm(2) and GIII (n = 5), lesion irradiated with 10 J/cm(2), and treated for 7 consecutive days with a laser He-Ne (lambda = 633 rim). After intracardiac perfusion, the muscles were dissected and reduced to small fragments, post-fixed in 1% osmium tetroxide, dehydrated in increasing alcohol concentrations, treated with propylene oxide and embedded in Spurr resin at 60 degrees C. Ultrafine Cuts examined on a transmission electron microscope (Jeol 1010) revealed in the control GI group a large number of altered Muscle fibers with degenerating mitochondria, intercellular substance containing degenerating cell fragments and budding blood capillaries with Underdeveloped endothelial cells. However, groups GII and GIII showed muscle fibers with few altered myofibrils, regularly contoured mitochondria, ample intermembrane spaces and dilated mitochondrial crests. The clean intercellular Substance showed numerous collagen fibers and capillaries with multiple abluminal processes, intraluminal protrusions and several pinocytic vesicles in endothelial cells. it was concluded that laser dosages of 5 or 10 J/cm(2) delivered by laser He-Ne (lambda = 633 rim) during 7 consecutive days increase mitochondrial activity in muscular fibers, activate fibroblasts and macrophages and stimulate angiogenesis, thus suggesting effectivity of laser therapy tinder these experimental conditions. (C) 2009 Elsevier Ltd. All rights reserved.

Mechanical comparative analysis of three different types of sutures in different dimensions tendons: experimental study

O objetivo da presente investigação experimental foi avaliar o perfil mecânico de três tipos de técnicas de sutura entre tendões de dimensões diferentes. Foram utilizados 21 cães sem raça definida (11machos/10 fêmeas), dos quais foram obtidos os tendões flexor comum dos dedos - t.c. (maior dimensão) e tibial cranial - t.cr. (menor dimensão), de ambos os membros pélvicos. Logo após a obtenção das peças foi realizada sutura, segundo cada tipo de técnica, porém sempre com o mesmo número de pontos. Os tendões utilizados para sutura foram sempre do lado direito e o controle do lado esquerdo (t.cr.). Após a sutura, os corpos de prova foram fixados em garras especialmente desenvolvidas e submetidos a ensaio de tração axial à velocidade de 30mm/minuto. Após o ensaio o programa da máquina forneceu os valores da carga máxima ( na ruptura) e deformação absoluta (mm) e relativa (%), além do diagrama carga-deformação. Os resultados foram submetidos a estudo estatístico pela análise de medidas repetidas no nível de 5% de significância. Não foi constatada diferença estatisticamente significativa nos parâmetros mecânicos avaliados nos três grupos de técnicas de suturas. em relação ao controle (tendão de menos diâmetro contra-lateral), observou-se que a sutura apresenta resistência máxima a tração significativamente menor que o controle e maior deformação.

Influence of educational level on myocardial hypertrophy of hemodialysis patients

Introduction: Chronic renal disease is associated with a high cardiovascular risk. Data from the general population associate cardiovascular diseases with low educational level, but no study has evaluated this association in patients on hemodialysis. Objective: This study aimed at evaluating the association between educational level, hypertension, and left ventricular hypertrophy in patients on chronic hemodialysis. Methods: A standard socioeconomic questionnaire was applied to 79 hemodialysis patients at the Hospital das Clínicas of Faculdade de Medicina de Botucatu, state of São Paulo. Clinical, laboratory and echocardiographic data were obtained from medical records. The patients were divided into two groups according to the median educational level, as follows: G1, patients with three or less years of schooling; G2, patients with more than three years of schooling. Results: Blood pressure, interdialytic weight gain, and variables statistically different in the two groups (p < 0.2) underwent multiple analysis. Independent associations were stated with p < 0.05 in multiple analysis. The mean age of patients was 57 ± 12.8 years, 46 were males (57%), and 53 white (67%). The variables selected for multiple analysis were: age (p = 0.004); educational level (p < 0.0001); body mass index (p = 0.124); left ventricular diameter (p = 0.048); and left ventricular mass index (p = 0.006). Antihypertensive drugs were similar in both groups. Systolic blood pressure (p = 0.006) and years of schooling (p = 0.047) had a significant and independent correlation with left ventricular mass index. Conclusion: In hemodialysis patients, left ventricular mass associated not only with blood pressure but also with educational level.

Is urine interleukin-8 level a reliable laboratory test for diagnosing late onset sepsis in premature infants?

The present study is aimed to determine serum and urine interleukin-8 (IL-8) levels in premature infants with late onset sepsis (LOS) and to evaluate if urine IL-8 is a useful test for LOS diagnosis. Fifty-six premature infants admitted to the NICU over 1 year had serum and urine IL-8 determined by ELISA. They were divided into three groups: I definite sepsis, II probable sepsis and III non-infected. Results were expressed as mean or median. Differences between groups were assessed by ANOVA, Kruskal-Wallis ANOVA and Dunns Method. Sensitivity, specificity and positive and negative predictive values were calculated and a receiver operator characteristic curve was constructed to determine serum and urine IL-8 accuracy. There were no differences between groups for birth weight, and gestational and post-natal age. Median serum and urine IL-8 levels were significantly higher in GI and GII: 929 x 906 x 625pg/ml; P=0.024, and 249 x 189 x 42pg/mgCr; P< 0.001. Optimal cut-off point was 625pg/ml for serum IL-8 with 69 sensitivity and 75pg/mgCr for urine IL-8 with 92 sensitivity. IL-8 can be determined in urine from premature infants with LOS and is an accurate and feasible diagnosis method.

Effect of the calcium level and limestone particle size on the performance of semi-heavy layers in the second cycle of egg production

An experiment was carried out at the Research and Development Unit of Brotas aiming at evaluating dietary calcium level and limestone particle size on the production performance of commercial (Hy-Line Brown) layers in the second lay cycle. Experiment duration was 112 days. A total number of 288 hens, with 83 weeks of age in the beginning of the experiment, were used in a completely randomized experimental design in a factorial arrangement of 2x3, with two calcium levels (3.5 and 4.0%) and three limestone particle size compositions: 100% fine limestone (FL), 30% coarse limestone (CL) + 70% fine limestone (FL), and 50% (CL) + 50% (FL), with six replicates of eight birds each. Egg weight (g), egg production (%), egg mass (%), feed intake (g), feed conversion ratio (kg/dz and kg/kg), mortality (%), and egg loss (%) were evaluated. The analysis of variance did not detect significant differences (p>0.05) among treatments on any of the evaluated performance parameters. It was concluded that the tested calcium levels and limestone particle composition did not influence the performance of semi-heavy layers in second production cycle.

Biomechanical evaluation of internal and external hexagon platform switched implant-abutment connections: An in vitro laboratory and three-dimensional finite element analysis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of low-level laser therapy on bone repair: Histological study in rats

Background and Objectives: Bone remodeling is characterized as a cyclic and lengthy process. It is currently accepted that not only this dynamics is triggered by a biological process, but also biochemical, electrical, and mechanical stimuli are key factors for the maintenance of bone tissue. The hypothesis that low-level laser therapy (LLLT) may favor bone repair has been suggested. The purpose of this study was to evaluate the bone repair in defects created in rat lower jaws after stimulation with infrared LLLT directly on the injured tissue.Study Design/Materials and Methods: Bone defects were prepared on the mandibles of 30 Holtzman rats allocated in two groups (n = 15), which were divided in three evaluation period (15, 45, and 60 days), with five animals each. control group-no treatment of the defect; laser group-single laser irradiation with a GaAlAs semiconductor diode laser device (lambda = 780 nm; P = 35 mW t = 40 s; circle minus = 1.0 mm; D = 178 J/cm(2); E = 1.4 J) directly on the defect area. The rats were sacrificed at the preestablished periods and the mandibles were removed and processed for staining with hematoxylin and eosin, Masson's Trichrome and picrosirius techniques.Results: the histological results showed bone formation in both groups. However, the laser group exhibited an advanced tissue response compared to the control group, abbreviating the initial inflammatory reaction and promoting rapid new bone matrix formation at 15 and 45 days (P < 0. 05). on the other hand, there were no significant differences between the groups at 60 days.Conclusion: the use of infrared LLLT directly to the injured tissue showed a biostimulating effect on bone remodeling by stimulating the modulation of the initial inflammatory response and anticipating the resolution to normal conditions at the earlier periods. However, there were no differences between the groups at 60 days.