Degradação dos fármacos ciprofloxacino e sertalina pelos processos ferro zero e foto-Fenton - aplicação em amostras de efluentes de estação de tratamento de esgoto

Pós-graduação em Química - IQ

A relationship between structural and electronic order-disorder effects and optical properties in crystalline TiO2 nanomaterials

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Measurement of differential cross sections for the production of a pair of isolated photons in pp collisions at root s=7TeV

A measurement of differential cross sections for the production of a pair of isolated photons in proton-proton collisions at root s = 7 TeV is presented. The data sample corresponds to an integrated luminosity of 5.0 fb(-1) collected with the CMS detector. A data-driven isolation template method is used to extract the prompt diphoton yield. The measured cross section for two isolated photons, with transverse energy above 40 and 25 GeV respectively, in the pseudorapidity range vertical bar eta vertical bar < 2.5, vertical bar eta vertical bar (sic) [1.44, 1.57] and with an angular separation Delta R > 0.45, is 17.2 +/-0.2 (stat) +/-1.9 (syst) +/- 0.4 (lumi) pb. Differential cross sections are measured as a function of the diphoton invariant mass, the diphoton transverse momentum, the azimuthal angle difference between the two photons, and the cosine of the polar angle in the Collins-Soper reference frame of the diphoton system. The results are compared to theoretical predictions at leading, next-to-leading, and next-to-next-to-leading order in quantum chromodynamics.

Local order and magnetic field effects on the electronic properties of disordered binary alloys in the quantum site percolation limit

Electronic properties of disordered binary alloys are studied via the calculation of the average Density of States (DOS) in two and three dimensions. We propose a new approximate scheme that allows for the inclusion of local order effects in finite geometries and extrapolates the behavior of infinite systems following finite-size scaling ideas. We particularly investigate the limit of the Quantum Site Percolation regime described by a tight-binding Hamiltonian. This limit was chosen to probe the role of short range order (SRO) properties under extreme conditions. The method is numerically highly efficient and asymptotically exact in important limits, predicting the correct DOS structure as a function of the SRO parameters. Magnetic field effects can also be included in our model to study the interplay of local order and the shifted quantum interference driven by the field. The average DOS is highly sensitive to changes in the SRO properties and striking effects are observed when a magnetic field is applied near the segregated regime. The new effects observed are twofold: there is a reduction of the band width and the formation of a gap in the middle of the band, both as a consequence of destructive interference of electronic paths and the loss of coherence for particular values of the magnetic field. The above phenomena are periodic in the magnetic flux. For other limits that imply strong localization, the magnetic field produces minor changes in the structure of the average DOS. © World Scientific Publishing Company.

Space–time zero-inflated count models of Harbor seals

Environmental data are spatial, temporal, and often come with many zeros. In this paper, we included space–time random effects in zero-inflated Poisson (ZIP) and ‘hurdle’ models to investigate haulout patterns of harbor seals on glacial ice. The data consisted of counts, for 18 dates on a lattice grid of samples, of harbor seals hauled out on glacial ice in Disenchantment Bay, near Yakutat, Alaska. A hurdle model is similar to a ZIP model except it does not mix zeros from the binary and count processes. Both models can be used for zero-inflated data, and we compared space–time ZIP and hurdle models in a Bayesian hierarchical model. Space–time ZIP and hurdle models were constructed by using spatial conditional autoregressive (CAR) models and temporal first-order autoregressive (AR(1)) models as random effects in ZIP and hurdle regression models. We created maps of smoothed predictions for harbor seal counts based on ice density, other covariates, and spatio-temporal random effects. For both models predictions around the edges appeared to be positively biased. The linex loss function is an asymmetric loss function that penalizes overprediction more than underprediction, and we used it to correct for prediction bias to get the best map for space–time ZIP and hurdle models.

GaMnAs: Position of Mn-d levels and majority spin band gap predicted from GGA-1/2 calculations

Among all magnetic semiconductors, GaMnAs seems to be the most important one. In this work, we present accurate first-principles calculations of GaMnAs within the GGA-1/2 approach: We concentrate our efforts in obtaining the position of the peak of Mn-d levels in the valence band and also the majority spin band gap. For the position of the Mn-d peak, we find a value of 3.3 eV below the Fermi level, in good agreement with the most recent experimental results of 3.5 and 3.7 eV. An analytical expression that fits the calculated E-g(x) for majority spin is derived in order to provide ready access to the band gap for the composition range from 0 to 0.25. We found a value of 3.9 eV for the gap bowing parameter. The results agree well with the most recent experimental data. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4718602]

The gender wage gap in developing and transition countries

The aim of my dissertation is to study the gender wage gap with a specific focus on developing and transition countries. In the first chapter I present the main existing theories proposed to analyse the gender wage gap and I review the empirical literature on the gender wage gap in developing and transition countries and its main findings. Then, I discuss the overall empirical issues related to the estimation of the gender wage gap and the issues specific to developing and transition countries. The second chapter is an empirical analysis of the gender wage gap in a developing countries, the Union of Comoros, using data from the multidimensional household budget survey “Enquete integrale auprès des ménages” (EIM) run in 2004. The interest of my work is to provide a benchmark analysis for further studies on the situation of women in the Comorian labour market and to contribute to the literature on gender wage gap in Africa by making available more information on the dynamics and mechanism of the gender wage gap, given the limited interest on the topic in this area of the world. The third chapter is an applied analysis of the gender wage gap in a transition country, Poland, using data from the Labour Force Survey (LSF) collected for the years 1994 and 2004. I provide a detailed examination of how gender earning differentials have changed over the period starting from 1994 to a more advanced transition phase in 2004, when market elements have become much more important in the functioning of the Polish economy than in the earlier phase. The main contribution of my dissertation is the application of the econometrical methodology that I describe in the beginning of the second chapter. First, I run a preliminary OLS and quantile regression analysis to estimate and describe the raw and conditional wage gaps along the distribution. Second, I estimate quantile regressions separately for males and females, in order to allow for different rewards to characteristics. Third, I proceed to decompose the raw wage gap estimated at the mean through the Oaxaca-Blinder (1973) procedure. In the second chapter I run a two-steps Heckman procedure by estimating a model of participation in the labour market which shows a significant selection bias for females. Forth, I apply the Machado-Mata (2005) techniques to extend the decomposition analysis at all points of the distribution. In Poland I can also implement the Juhn, Murphy and Pierce (1991) decomposition over the period 1994-2004, to account for effects to the pay gap due to changes in overall wage dispersion beyond Oaxaca’s standard decomposition.

Study of silicon-on-insulator multiple-gate MOS structures including band-gap engineering and self heating effects

The progresses of electron devices integration have proceeded for more than 40 years following the well–known Moore’s law, which states that the transistors density on chip doubles every 24 months. This trend has been possible due to the downsizing of the MOSFET dimensions (scaling); however, new issues and new challenges are arising, and the conventional ”bulk” architecture is becoming inadequate in order to face them. In order to overcome the limitations related to conventional structures, the researchers community is preparing different solutions, that need to be assessed. Possible solutions currently under scrutiny are represented by: • devices incorporating materials with properties different from those of silicon, for the channel and the source/drain regions; • new architectures as Silicon–On–Insulator (SOI) transistors: the body thickness of Ultra-Thin-Body SOI devices is a new design parameter, and it permits to keep under control Short–Channel–Effects without adopting high doping level in the channel. Among the solutions proposed in order to overcome the difficulties related to scaling, we can highlight heterojunctions at the channel edge, obtained by adopting for the source/drain regions materials with band–gap different from that of the channel material. This solution allows to increase the injection velocity of the particles travelling from the source into the channel, and therefore increase the performance of the transistor in terms of provided drain current. The first part of this thesis work addresses the use of heterojunctions in SOI transistors: chapter 3 outlines the basics of the heterojunctions theory and the adoption of such approach in older technologies as the heterojunction–bipolar–transistors; moreover the modifications introduced in the Monte Carlo code in order to simulate conduction band discontinuities are described, and the simulations performed on unidimensional simplified structures in order to validate them as well. Chapter 4 presents the results obtained from the Monte Carlo simulations performed on double–gate SOI transistors featuring conduction band offsets between the source and drain regions and the channel. In particular, attention has been focused on the drain current and to internal quantities as inversion charge, potential energy and carrier velocities. Both graded and abrupt discontinuities have been considered. The scaling of devices dimensions and the adoption of innovative architectures have consequences on the power dissipation as well. In SOI technologies the channel is thermally insulated from the underlying substrate by a SiO2 buried–oxide layer; this SiO2 layer features a thermal conductivity that is two orders of magnitude lower than the silicon one, and it impedes the dissipation of the heat generated in the active region. Moreover, the thermal conductivity of thin semiconductor films is much lower than that of silicon bulk, due to phonon confinement and boundary scattering. All these aspects cause severe self–heating effects, that detrimentally impact the carrier mobility and therefore the saturation drive current for high–performance transistors; as a consequence, thermal device design is becoming a fundamental part of integrated circuit engineering. The second part of this thesis discusses the problem of self–heating in SOI transistors. Chapter 5 describes the causes of heat generation and dissipation in SOI devices, and it provides a brief overview on the methods that have been proposed in order to model these phenomena. In order to understand how this problem impacts the performance of different SOI architectures, three–dimensional electro–thermal simulations have been applied to the analysis of SHE in planar single and double–gate SOI transistors as well as FinFET, featuring the same isothermal electrical characteristics. In chapter 6 the same simulation approach is extensively employed to study the impact of SHE on the performance of a FinFET representative of the high–performance transistor of the 45 nm technology node. Its effects on the ON–current, the maximum temperatures reached inside the device and the thermal resistance associated to the device itself, as well as the dependence of SHE on the main geometrical parameters have been analyzed. Furthermore, the consequences on self–heating of technological solutions such as raised S/D extensions regions or reduction of fin height are explored as well. Finally, conclusions are drawn in chapter 7.

New path integral simulation algorithms and their application to creep in the quantum sine-Gordon chain

A path integral simulation algorithm which includes a higher-order Trotter approximation (HOA)is analyzed and compared to an approach which includes the correct quantum mechanical pair interaction (effective Propagator (EPr)). It is found that the HOA algorithmconverges to the quantum limit with increasing Trotter number P as P^{-4}, while the EPr algorithm converges as P^{-2}.The convergence rate of the HOA algorithm is analyzed for various physical systemssuch as a harmonic chain,a particle in a double-well potential, gaseous argon, gaseous helium and crystalline argon. A new expression for the estimator for the pair correlation function in the HOA algorithm is derived. A new path integral algorithm, the hybrid algorithm, is developed.It combines an exact treatment of the quadratic part of the Hamiltonian and thehigher-order Trotter expansion techniques.For the discrete quantum sine-Gordon chain (DQSGC), it is shown that this algorithm works more efficiently than all other improved path integral algorithms discussed in this work. The new simulation techniques developed in this work allow the analysis of theDQSGC and disordered model systems in the highly quantum mechanical regime using path integral molecular dynamics (PIMD)and adiabatic centroid path integral molecular dynamics (ACPIMD).The ground state phonon dispersion relation is calculated for the DQSGC by the ACPIMD method.It is found that the excitation gap at zero wave vector is reduced by quantum fluctuations. Two different phases exist: One phase with a finite excitation gap at zero wave vector, and a gapless phase where the excitation gap vanishes.The reaction of the DQSGC to an external driving force is analyzed at T=0.In the gapless phase the system creeps if a small force is applied, and in the phase with a gap the system is pinned. At a critical force, the systems undergo a depinning transition in both phases and flow is induced. The analysis of the DQSGC is extended to models with disordered substrate potentials. Three different cases are analyzed: Disordered substrate potentials with roughness exponent H=0, H=1/2,and a model with disordered bond length. For all models, the ground state phonon dispersion relation is calculated.

Numeralklassifikatoren im Thai

Wie viele andere Sprachen Ost- und Südostasiens ist das Thai eine numerusneutrale Sprache, in der ein Nomen lediglich das Konzept benennt und keinen Hinweis auf die Anzahl der Objekte liefert. Um Nomina im Thai zählen zu können, ist der Klassifikator (Klf) nötig, der die Objekte anhand ihrer semantischen Schlüsseleigenschaft herausgreift und individualisiert. Neben der Klassifikation stellt die Individualisierung die Hauptfunktion des Klf dar. Weitere Kernfunktionen des Klf außerhalb des Zählkontextes sind die Markierung der Definitheit, des Numerus sowie des Kontrasts. Die wichtigsten neuen Ergebnisse dieser Arbeit, die sowohl die Ebenen der Grammatik und Semantik als auch die der Logik und Pragmatik integriert, sind folgende: Im Thai kann der Klf sowohl auf der Element- als auch auf der Mengenebene agieren. In der Verbindung mit einem Demonstrativ kann der Klf auch eine pluralische Interpretation hervorrufen, wenn er auf eine als pluralisch präsupponierte Gesamtmenge referiert oder die Gesamtmenge in einer Teil-Ganzes-Relation individualisiert. In einem Ausdruck, der bereits eine explizite Zahlangabe enthält, bewirkt die Klf-Demonstrativ-Konstruktion eine Kontrastierung von Mengen mit gleichen Eigenschaften. Wie auch der Individualbegriff besitzt der Klf Intension und Extension. Intension und Extension von Thai-Klf verhalten sich umgekehrt proportional, d.h. je spezifischer der Inhalt eines Klf ist, desto kleiner ist sein Umfang. Der Klf signalisiert das Schlüsselmerkmal, das mit der Intension des Nomens der Identifizierung des Objekts dient. Der Klf individualisiert das Nomen, indem er Teilmengen quantifiziert. Er kann sich auf ein Objekt, eine bestimmte Anzahl von Objekten oder auf alle Objekte beziehen. Formal logisch lassen sich diese Funktionen mithilfe des Existenz- und des Allquantors darstellen. Auch die Nullstelle (NST) läßt sich formal logisch darstellen. Auf ihren jeweiligen Informationsgehalt reduziert, ergeben sich für Klf und NST abhängig von ihrer Positionierung verschiedene Informationswerte: Die Opposition von Klf und NST bewirkt in den Fragebögen ausschließlich skalare Q-Implikaturen, die sich durch die Informationsformeln in Form einer Horn-Skala darstellen lassen. In einem sich aufbauenden Kontext transportieren sowohl Klf als auch NST in der Kontextmitte bekannte Informationen, wodurch Implikaturen des M- bzw. I-Prinzips ausgelöst werden. Durch die Verbindung der Informationswerte mit den Implikaturen des Q-, M- und I-Prinzips lässt sich anhand der Positionierung direkt erkennen, wann der Klf die Funktion der Numerus-, der Definitheits- oder der Kontrast-Markierung erfüllt.

Tracing of 15N in a mountain spruce forest: comparison of experimental data with th TRACE model

Despite numerous studies about nitrogen-cycling in forest ecosystems, many uncertainties remain, especially regarding the longer-term nitrogen accumulation. To contribute to filling this gap, the dynamic process-based model TRACE, with the ability to simulate 15N tracer redistribution in forest ecosystems was used to study N cycling processes in a mountain spruce forest of the northern edge of the Alps in Switzerland (Alptal, SZ). Most modeling analyses of N-cycling and C-N interactions have very limited ability to determine whether the process interactions are captured correctly. Because the interactions in such a system are complex, it is possible to get the whole-system C and N cycling right in a model without really knowing if the way the model combines fine-scale interactions to derive whole-system cycling is correct. With the possibility to simulate 15N tracer redistribution in ecosystem compartments, TRACE features a very powerful tool for the validation of fine-scale processes captured by the model. We first adapted the model to the new site (Alptal, Switzerland; long-term low-dose N-amendment experiment) by including a new algorithm for preferential water flow and by parameterizing of differences in drivers such as climate, N deposition and initial site conditions. After the calibration of key rates such as NPP and SOM turnover, we simulated patterns of 15N redistribution to compare against 15N field observations from a large-scale labeling experiment. The comparison of 15N field data with the modeled redistribution of the tracer in the soil horizons and vegetation compartments shows that the majority of fine-scale processes are captured satisfactorily. Particularly, the model is able to reproduce the fact that the largest part of the N deposition is immobilized in the soil. The discrepancies of 15N recovery in the LF and M soil horizon can be explained by the application method of the tracer and by the retention of the applied tracer by the well developed moss layer, which is not considered in the model. Discrepancies in the dynamics of foliage and litterfall 15N recovery were also observed and are related to the longevity of the needles in our mountain forest. As a next step, we will use the final Alptal version of the model to calculate the effects of climate change (temperature, CO2) and N deposition on ecosystem C sequestration in this regionally representative Norway spruce (Picea abies) stand.

NLO thermal dilepton rate at non-zero momentum

The vector channel spectral function and the dilepton production rate from a QCD plasma at a temperature above a few hundred MeV are evaluated up to next-to-leading order (NLO) including their dependence on a non-zero momentum with respect to the heat bath. The invariant mass of the virtual photon is taken to be in the range K2 ~ (πT)2 ~ (1GeV)2, generalizing previous NLO results valid for K2 ≫ (πT)2. In the opposite regime 0 < K2 ≪ (πT)2 the loop expansion breaks down, but agrees nevertheless in order of magnitude with a previous result obtained through resummations. Ways to test the vector spectral function through comparisons with imaginary-time correlators measured on the lattice are discussed.

SIGNALING MECHANISMS THAT CONTROL GAP JUNCTIONAL COUPLING BETWEEN RETINAL NEURONS

Gap junctions between neurons form the structural substrate for electrical synapses. Connexin 36 (Cx36, and its non-mammalian ortholog connexin 35) is the major neuronal gap junction protein in the central nervous system (CNS), and contributes to several important neuronal functions including neuronal synchronization, signal averaging, network oscillations, and motor learning. Connexin 36 is strongly expressed in the retina, where it is an obligatory component of the high-sensitivity rod photoreceptor pathway. A fundamental requirement of the retina is to adapt to broadly varying inputs in order to maintain a dynamic range of signaling output. Modulation of the strength of electrical coupling between networks of retinal neurons, including the Cx36-coupled AII amacrine cell in the primary rod circuit, is a hallmark of retinal luminance adaptation. However, very little is known about the mechanisms regulating dynamic modulation of Cx36-mediated coupling. The primary goal of this work was to understand how cellular signaling mechanisms regulate coupling through Cx36 gap junctions. We began by developing and characterizing phospho-specific antibodies against key regulatory phosphorylation sites on Cx36. Using these tools we showed that phosphorylation of Cx35 in fish models varies with light adaptation state, and is modulated by acute changes in background illumination. We next turned our focus to the well-studied and readily identifiable AII amacrine cell in mammalian retina. Using this model we showed that increased phosphorylation of Cx36 is directly related to increased coupling through these gap junctions, and that the dopamine-stimulated uncoupling of the AII network is mediated by dephosphorylation of Cx36 via protein kinase A-stimulated protein phosphatase 2A activity. We then showed that increased phosphorylation of Cx36 on the AII amacrine network is driven by depolarization of presynaptic ON-type bipolar cells as well as background light increments. This increase in phosphorylation is mediated by activation of extrasynaptic NMDA receptors associated with Cx36 gap junctions on AII amacrine cells and by Ca2+-calmodulin-dependent protein kinase II activation. Finally, these studies indicated that coupling is regulated locally at individual gap junction plaques. This work provides a framework for future study of regulation of Cx36-mediated coupling, in which increased phosphorylation of Cx36 indicates increased neuronal coupling.

Excitonic Splitting, Delocalization, and Vibronic Quenching in the Benzonitrile Dimer

The excitonic S1/S2 state splitting and the localization/delocalization of the S1 and S2 electronic states are investigated in the benzonitrile dimer (BN)2 and its 13C and d5 isotopomers by mass-resolved two-color resonant two-photon ionization spectroscopy in a supersonic jet, complemented by calculations. The doubly hydrogen-bonded (BN-h5)2 and (BN-d5)2 dimers are C2h symmetric with equivalent BN moieties. Only the S0 → S2 electronic origin is observed, while the S0 → S1 excitonic component is electric-dipole forbidden. A single 12C/13C or 5-fold h5/d5 isotopic substitution reduce the dimer symmetry to Cs, so that the heteroisotopic dimers (BN)2-(h5 – h513C), (BN)2-(h5 – d5), and (BN)2-(h5 – h513C) exhibit both S0 → S1 and S0 → S2 origins. Isotope-dependent contributions Δiso to the excitonic splittings arise from the changes of the BN monomer zero-point vibrational energies; these range from Δiso(12C/13C) = 3.3 cm–1 to Δiso(h5/d5) = 155.6 cm–1. The analysis of the experimental S1/S2 splittings of six different isotopomeric dimers yields the S1/S2 exciton splitting Δexc = 2.1 ± 0.1 cm–1. Since Δiso(h5/d5) ≫ Δexc and Δiso(12C/13C) > Δexc, complete and near-complete exciton localization occurs upon 12C/13C and h5/d5 substitutions, respectively, as diagnosed by the relative S0 → S1 and S0 → S2 origin band intensities. The S1/S2 electronic energy gap of (BN)2 calculated by the spin-component scaled approximate second-order coupled-cluster (SCS-CC2) method is Δelcalc = 10 cm–1. This electronic splitting is reduced by the vibronic quenching factor Γ. The vibronically quenched exciton splitting Δelcalc·Γ = Δvibroncalc = 2.13 cm–1 is in excellent agreement with the observed splitting Δexc = 2.1 cm–1. The excitonic splittings can be converted to semiclassical exciton hopping times; the shortest hopping time is 8 ps for the homodimer (BN-h5)2, the longest is 600 ps for the (BN)2(h5 – d5) heterodimer.

Dynamic computer simulation of electrophoretic enantiomer migration order and separation in presence of a neutral cyclodextrin

One-dimensional dynamic computer simulation was employed to investigate the separation and migration order change of ketoconazole enantiomers at low pH in presence of increasing amounts of (2-hydroxypropyl)-β-cyclodextrin (OHP-β-CD). The 1:1 interaction of ketoconazole with the neutral cyclodextrin was simulated under real experimental conditions and by varying input parameters for complex mobilities and complexation constants. Simulation results obtained with experimentally determined apparent ionic mobilities, complex mobilities, and complexation constants were found to compare well with the calculated separation selectivity and experimental data. Simulation data revealed that the migration order of the ketoconazole enantiomers at low (OHP-β-CD) concentrations (i.e. below migration order inversion) is essentially determined by the difference in complexation constants and at high (OHP-β-CD) concentrations (i.e. above migration order inversion) by the difference in complex mobilities. Furthermore, simulations with complex mobilities set to zero provided data that mimic migration order and separation with the chiral selector being immobilized. For the studied CEC configuration, no migration order inversion is predicted and separations are shown to be quicker and electrophoretic transport reduced in comparison to migration in free solution. The presented data illustrate that dynamic computer simulation is a valuable tool to study electrokinetic migration and separations of enantiomers in presence of a complexing agent.