Estudo químico-computacional da reatividade de aziridinona e diaziridinona através de cálculos semi-empíricos

The results of semiempirical molecular orbital calculations performed on aziridinone and diaziridinone employing the MNDO, AM1, and PM3 molecular models are presented. The AM1 method, which best reproduces ground-state molecular properties, is used to calculate electronic parameters and the use of these parameters for the evaluation of reactivity is discussed.

Software Licensing: Implementing Electronic Licensing in Medical Technology Company

The purpose of this thesis is to examine software licensing, how a software developer can benefit from it and to define specifications for licensing system of software based medical technology product. The thesis has been divided into theoretical and empirical parts. In the theoretical part the concept of software licensing and different aspects that are connected to it are examined with a help of research material. On the ground of this research, in the empirical part, a licensing system for a medical software product called iCentral is designed. The empirical part is based on interviews, questionnaire and on authors own experience gained while working for the case-company.The thesis has great practical importance for the case-company by proposing both an ideal, and more importantly, practical implementation for a licensing system of a product. Thesis shows that electronic licensing is a viable option to sell medical technology products without a need to revise existing procedures or the enterprise resource system in the case company.

Defects in Persistent Luminescence Materials

Persistent luminescence materials can store energy from solar radiation or artificial lighting and release it over a period of several hours without a continuous excitation source. These materials are widely used to improve human safety in emergency and traffic signalization. They can also be utilized in novel applications including solar cells, medical diagnostics, radiation detectors and structural damage sensors. The development of these materials is currently based on methods based on trial and error. The tailoring of new materials is also hindered by the lack of knowledge on the role of their intrinsic and extrinsic lattice defects in the appropriate mechanisms. The goal of this work was to clarify the persistent luminescence mechanisms by combining ab initio density functional theory (DFT) calculations with selected experimental methods. The DFT approach enables a full control of both the nature of the defects and their locations in the host lattice. The materials studied in the present work, the distrontium magnesium disilicate (Sr₂MgSi₂O₇) and strontium aluminate (SrAl₂O₄) are among the most efficient persistent luminescence hosts when doped with divalent europium Eu²⁺ and co-doped with trivalent rare earth ions R³⁺ (R: Y, La-Nd, Sm, Gd-Lu). The polycrystalline materials were prepared with the solid state method and their structural and phase purity was confirmed by X-ray powder diffraction. Their local crystal structure was studied by high-resolution transmission electron microscopy. The crystal and electronic structure of the nondoped as well as Eu²⁺, R^2+/3+ and other defect containing materials were studied using DFT calculations. The experimental trap depths were obtained using thermoluminescence (TL) spectroscopy. The emission and excitation of Sr₂MgSi₂O₇:Eu²+,Dy³⁺ were also studied. Significant modifications in the local crystal structure due to the Eu²⁺ ion and lattice defects were found by the experimental and DFT methods. The charge compensation effects induced by the R³⁺ co-doping further increased the number of defects and distortions in the host lattice. As for the electronic structure of Sr₂MgSi₂O₇ and SrAl₂O₄, the experimental band gap energy of the host materials was well reproduced by the calculations. The DFT calculated Eu²⁺ and R^2+/3+ 4fn as well as 4f^n-15d¹ ground states in the Sr₂MgSi₂O₇ band structure provide an independent verification for an empirical model which is constructed using rather sparse experimental data for the R³⁺ and especially the R²⁺ ions. The intrinsic and defect induced electron traps were found to act together as energy storage sites contributing to the materials’ efficient persistent luminescence. The calculated trap energy range agreed with the trap structure of Sr₂MgSi₂O₇ obtained using TL measurements. More experimental studies should be carried out for SrAl₂O₄ to compare with the DFT calculations. The calculated and experimental results show that the electron traps created by both the rare earth ions and vacancies are modified due to the defect aggregation and charge compensation effects. The relationships between this modification and the energy storage properties of the solid state materials are discussed.

Turgida turgida (Nematoda: Physalopteridae) parasitic in white-bellied opossum, Didelphis albiventris (Marsupialia: Didelphidae), state of Mato Grosso do Sul, Brazil

Turgida turgida have been largely reported parasitizing Didelphis species in North and South America based on light microscopy observation. However, the features that differentiate T. turgida from other physalopterid species should be observed using scanning electron microscopy (SEM). A female white-bellied opossum, Didelphis albiventris, arrived dead at the Centro de Reabilitação de Animais Silvestres (CRAS) in the municipality of Campo Grande, state of Mato Grosso do Sul, Brazil. During the necropsy, adult nematodes were collected from stomach and intestine. The nematodes were determined to be adult specimens and submitted to SEM for the species determination. This is the first report of T. turgida confirmed by SEM in the Neotropical region and the first report in an urban area in the state of Mato Grosso do Sul, Brazil.

Additional information about a mange outbreak by Allopsoroptoides galli (Acari: Psoroptoididae) in commercial laying hens in the state of São Paulo, Brazil

This paper reports additional information about a mange outbreak by the mite Allopsoroptoides galli in a commercial egg-laying hen facility in the state of São Paulo, Brazil. About half of the 76,000 multi-age birds of the flock were affected. Experimental infestations carried out on naive hens resulted in clinical signs similar to those diagnosed in naturally infested hens, such as generalized scaly dermatitis, presence of mucus-like material and yellowish crusts on the skin and around the calami, feather loss and strong unpleasant odor. About 30% drop of egg production was estimated. The possible source of infestation were wild birds identified on the ground and roofs of the sheds.

A high frequency electronic transducer for multiphase flow measurements

This paper describes an electronic transducer for multiphase flow measurement. Its high sensitivity, good signal to noise ratio and accuracy are achieved through an electrical impedance sensor with a special guard technique. The transducer consists of a wide bandwidth and high slew rate differentiator where the lead inductance and stray capacitance effects are compensated. The sensor edge effect is eliminated by using a guard electrode based on the virtual ground potential of the operational amplifier. A theoretical modeling and a calibration method are also presented. The results obtained seem to confirm the validity of the proposed technique.

Influence of edaphic variables on the floristic composition and structure of the tree-shrub vegetation in typical and rocky outcrop cerrado areas in Serra Negra, Goiás State, Brazil

The present study analyzed the influence of edaphic variables on the floristic compositions and structures of the arboreal and shrub vegetation of typical cerrado (TC) and rocky outcrop cerrado (RC) communities in the Serra Negra mountain range in Piranhas Municipality, Goiás State, Brazil. Ten 20×50m plots were established in each community, and all individuals with minimum diameters ³5cm measured at 30cm above soil level were sampled. Composite soil samples were collected at 0-20cm depths in each plot for physical and chemical analyses. The proportions of above-ground rock cover work also estimated in each RC plot. A total of 2,009 individuals (83 species, 69 genera, and 34 families) were recorded. Qualea parviflora was the only species consistently among the 10 most structurally important taxa in both communities, and was considered a generalist species. The observed and estimated species richnesses were greater in RC than in TC, although plant basal areas and heights did not differ between them. There were positive correlations between rock cover×plant density and rock cover×basal areas. TWINSPAN and PCA analysis separated the TC and RC plots, and three RC habitat specialist species (Wunderlichia mirabilis, Norantea guianensis, and Tibouchina papyrus) were identified. Soil variables were found to have greater effects on the species compositions of the TC and RC sites than the geographic distances between sampling plots. According to CCA analysis, the exclusive (or more abundant species) of each community were correlated with soil variables, and these variables therefore determined the selection of some species and influenced the differentiation of the vegetation structures of the communities studied.

Solid-state reference and ion-selective electrodes : towards portable potentiometric sensing

Potentiometric sensors are very attractive tools for chemical analysis because of their simplicity, low power consumption and low cost. They are extensively used in clinical diagnostics and in environmental monitoring. Modern applications of both fields require improvements in the conventional construction and in the performance of the potentiometric sensors, as the trends are towards portable, on-site diagnostics and autonomous sensing in remote locations. The aim of this PhD work was to improve some of the sensor properties that currently hamper the implementation of the potentiometric sensors in modern applications. The first part of the work was concentrated on the development of a solid-state reference electrode (RE) compatible with already existing solid-contact ion-selective electrodes (ISE), both of which are needed for all-solid-state potentiometric sensing systems. A poly(vinyl chloride) membrane doped with a moderately lipophilic salt, tetrabutylammonium-tetrabutylborate (TBA-TBB), was found to show a satisfactory stability of potential in sample solutions with different concentrations. Its response time was nevertheless slow, as it required several minutes to reach the equilibrium. The TBA-TBB membrane RE worked well together with solid-state ISEs in several different situations and on different substrates enabling a miniature design. Solid contacts (SC) that mediate the ion-to-electron transduction are crucial components of well-functioning potentiometric sensors. This transduction process converting the ionic conduction of an ion-selective membrane to the electronic conduction in the circuit was studied with the help of electrochemical impedance spectroscopy (EIS). The solid contacts studied were (i) the conducting polymer (CP) poly(3,4-ethylienedioxythiophene) (PEDOT) and (ii) a carbon cloth having a high surface area. The PEDOT films were doped with a large immobile anion poly(styrene sulfonate) (PSS-) or with a small mobile anion Cl-. As could be expected, the studied PEDOT solid-contact mediated the ion-toelectron transduction more efficiently than the bare glassy carbon substrate, onto which they were electropolymerized, while the impedance of the PEDOT films depended on the mobility of the doping ion and on the ions in the electrolyte. The carbon cloth was found to be an even more effective ion-to-electron transducer than the PEDOT films and it also proved to work as a combined electrical conductor and solid contact when covered with an ion-selective membrane or with a TBA-TBB-based reference membrane. The last part of the work was focused on improving the reproducibility and the potential stability of the SC-ISEs, a problem that culminates to the stability of the standard potential E°. It was proven that the E° of a SC-ISE with a conducting polymer as a solid contact could be adjusted by reducing or oxidizing the CP solid contact by applying current pulses or a potential to it, as the redox state of the CP solid-contact influences the overall potential of the ISE. The slope and thus the analytical performance of the SC-ISEs were retained despite the adjustment of the E°. The shortcircuiting of the SC-ISE with a conventional large-capacitance RE was found to be a feasible instrument-free method to control the E°. With this method, the driving force for the oxidation/reduction of the CP was the potential difference between the RE and the SC-ISE, and the position of the adjusted potential could be controlled by choosing a suitable concentration for the short-circuiting electrolyte. The piece-to-piece reproducibility of the adjusted potential was promising, and the day-today reproducibility for a specific sensor was excellent. The instrumentfree approach to control the E° is very attractive considering practical applications.

Global instability of currencies: reasons and perspectives according to the state-corporation hegemonic stability theory

This paper analyses reasons of the instability of the world monetary system. The author considers this problem from historical and contemporary perspectives. According to presented point of view banknotes and electronic money which replaced gold and silver coins in popular circulation are the most important reason of the instability. There are also proven positive and negative consequences of money instability. Reforms of the world monetary system need agreement within the global collective hegemony of state-powers and transnational corporations.

The battle over deficits : the struggle to maintain Canada's social welfare state : a thesis /

Abstract This thesis seeks to answer a number of questions concerning the deficit and debt in Canada. It focuses pri.arily on the federal level of government but with SOBe discussion of provincial governaent policy as well. In ~997, Canada's federal debt caae close ro six hundred billion dollars - $594 billion or 74.4 % of Gross Do.estic Product (GDP) to be exact. The purpose of this theses is threefold: To find out why Canada accu.ulated such a debt, to discover if there is a so-called debt crisis; and to discover if it is possible to preserve Canada's national welfare state given the financial restraints that have been adopted by both federal and provincial governments. Politicians are torn between economist' two contrasting views regarding deficits: Neo-Keynesian and neo-conservative. The neoKeynesian school focuses al1llOst exclusively on the short term stability of the economy and tends to dismiss concerns regarding the level of debt. Neo conservatives focus almost exclusively on the perceived costs of growth in the national debt and are willing to forego any stabilization benefits to ensure that the debt is controlled. These polar view do have one thing in coa.on; both confix-. that deficits influence govermaent policies. Both of these econoBic theories will have far-reaching influences on the federal gover1lJlJent's decision-making process. These economic theories will be discussed throughout this thesis.

The neo-liberal state and the crisis of public service broadcasting in the Anglo-American democracies /

The NeO'liberal State and the Crisis ofPublic Service Broadcasting in the Anglo-American Democracies The purpose ofthis analysis ofthe present condition ofpublic service broadcasting in the Anglo- American democracies was to investigate whether such media can still be regarded as the primarypublic spherefor a dialogue between each nation 's civil society and the State. The motivationfor this thesis was based on a presumption that such fora for public discussion on the central issues of each society have become viewed as less relevant bypoliticians andpolicy-makers and thepublics they were intended to serve in the Anglo-American democracies over thepast two decades. It is speculated that this is the case because ofa beliefthat the post-war consensus between the respective States andpublics that led to the construction of the Keynesian Welfare State and the notion ofpublic service broadcasting has been displaced by an individualistic, neo-liberal, laissez-faire ideology. In other words, broadcasting as a consumer-oriented, commercial commodity has superseded concerns pertaining to the importance ofthe public interest. The methodology employed in this thesis is a comparative analysisfrom a criticalpolitical economy perspective. It was considered appropriate to focus on the United Kingdom, Australia, Canada and the\ United States because they comprise the four largest Anglo-American nations with democratic political systems andprimarily market economies. Justificationfor this particular sample is reinforced by thefact that case study countries also share a common socio-political and economic tradition. The evidence assembledfor this thesis consisted almost exclusively ofexisting literature on the subjects ofpublic service broadcasting, global economic andpolitical integration, and the ascendance ofthe 'free-market ' ethos in Western democracies since the late mid- to late-1970s. In essence, this thesis could be considered as a reinterpretation ofthe existing literature relevant to these issues. Several important common features werefound among the political, economic and broadcasting systems of the four case study nations. It is proposed that the prevalence of the neo-liberal world view throughout the political and policy environments of the four countries has undermined the stability and credibility of each nation 's national public service broadcasting organization, although with varying intensity and effect,. Deregulation ofeach nation 's broadcasting system and the supremacy ofthe notion of 'consumer sovereignty' have marginalized the view of broadcasting on any basis other than strictly economic criteria in thefour case study countries. This thesis concludes that,for a reconstruction ofa trulyparticipatory anddemocraticpublicsphere to be realized in the present as well as thefuture, a reassessment ofthe conventional concept ofthe 'public sphere ' is necessary. Therefore, it is recommended that thefocus ofpolicy-makers in each Anglo-American democracy be redirectedfrom that which conceived ofan all-encompassing, large, state-ownedand operated public broadcasting service toward a view which considers alternativeforms ofpublic communication, such as local community and ethnic broadcasting operations, that are likely to be more responsive to the needs of the increasingly diverse and heterogeneous populations that comprise the modem Anglo-American democracies. The traditional conception of public broadcasters must change in accordance with its contemporary environment if the fundamental principles of the public sphere and public service broadcasting are to be realized.

From the ground up : understanding how teachers and administrators make sense of tension

Strategies designed to improve educational systems have created tensions in school personnel as they struggle to respond to competing demands of ongoing change within their daily realities. The purpose of this case study was to investigate how teachers and administrators in one elementary school made sense ofthese tensions and to explore the factors that constrained or shaped their responses. A constructive interpretative case study using a grounded theory approach was used. Qualitative data were collected through document analysis, semi-structured interviews, and participant observation. In-depth information about teachers' and administrators' experiences and a contextual understanding oftension was generated from inductive analysis of the data. The study found that tension was a phenomenon situated in the context in which it arose. A contextual understanding of tension revealed the interactions between the institutional, personal, and emotional domains that continually shaped individual and group behavioural responses. This contextual understanding of tension provided the means to reinterpret resistance to change. It also helped to show how teachers and administrators reconstructed identities and made sense in context.. Of particular note was the crucial nature of the conditions under which teachers and adlninistrators shaped meaning and understood change. This study sheds light on the contextual intricacies of tension that may help leaders with the complex design and implementation of educational change..

Synechococcus sp. PCC 7002 CpcB lyase null mutations alter phycocyanin chromophore function and, consequently, affect the redistribution of excitation energy via the light state transition /

Phycobilisomes are the major light harvesting complexes for cyanobacteria and phycocyanin is the primary phycobiliprotein of the phycobilisome rod. The phycocyanobilin lyases responsible for chromophorylating the phycocyanin p subunit (CpcB) have been recently identified in the cyanobacterium Synechococcus sp. PCC 7002. Surprisingly, mutants missing the CpcB lyases were nevertheless capable of producing pigmented phycocyanin. 10K absorbance measurements revealed that the energy states of the p phycocyanin chromophores were only subtly shifted; however, 77K steady state fluorescence emission spectroscopy showed excitation energy transfer involving the targeted chromophores to be highly disrupted. Such evidence suggests that phycobilin orientation within the binding domain is specifically modified. We hypothesized that alternate, less specific lyases are able to act on the p binding sites. A phycocyanin linker-polypeptide deficient mutant was similarly characterized. The light state transition, a short term adaptation of the photosynthetic light harvesting apparatus resulting in the redistribution of excitation energy among the photo systems, was shown to be dominated by the reallocation of phycocyanin-absorbed excitation energy. Treatment with a high M phosphate buffer effectively prevented the redistribution of both chlorophyll a- and phycobilisome- absorbed excitation energy, suggesting that the two effects are not strictly independent. The mutant strains required a larger redistribution of excitation energy between light states, perhaps to compensate for their loss in phycobilisome antenna function.

The near ultraviolet absorption spectrum of phosgene /

The near ultraviolet absorption of phosgene has been assigned to a * 1 1 ~.--n, A;-- Al electronic transition from vapour phase spectra recorded under conditions of high resolution and low_t~mperature. Progressions in Vi, v2' V3' V4 and V4 ha\1e been identified in the spectrum and have been analyzed in terms of vibronic transitions between a planar ground and a nonplanar excited state. A ba~rier height of 3170 cm~l:and a nona planar equilibrium angle of 32.5 were calculated for the upper state from a fit of the energy levels of a Lorentzian-guadratic potential func- ~ion to the observed levels of V 4 . ' ~he false ori- 3in, 41 0 , of the spectrum has been assigned to the band at 33,631 cm -1 . An oscillator strength of -3 1 . 1 f = 1. a x 10 has been obtained for the A - A 2 1 transition.

Application of [Lambda] to the fourth perturbation theory in calculating the equation of state of rare gas solids and fcc metals

We have calculated the thermodynamic properties of monatomic fcc crystals from the high temperature limit of the Helmholtz free energy. This equation of state included the static and vibrational energy components. The latter contribution was calculated to order A4 of perturbation theory, for a range of crystal volumes, in which a nearest neighbour central force model was used. We have calculated the lattice constant, the coefficient of volume expansion, the specific heat at constant volume and at constant pressure, the adiabatic and the isothermal bulk modulus, and the Gruneisen parameter, for two of the rare gas solids, Xe and Kr, and for the fcc metals Cu, Ag, Au, Al, and Pb. The LennardJones and the Morse potential were each used to represent the atomic interactions for the rare gas solids, and only the Morse potential was used for the fcc metals. The thermodynamic properties obtained from the A4 equation of state with the Lennard-Jones potential, seem to be in reasonable agreement with experiment for temperatures up to about threequarters of the melting temperature. However, for the higher temperatures, the results are less than satisfactory. For Xe and Kr, the thermodynamic properties calculated from the A2 equation of state with the Morse potential, are qualitatively similar to the A 2 results obtained with the Lennard-Jones potential, however, the properties obtained from the A4 equation of state are in good agreement with experiment, since the contribution from the A4 terms seem to be small. The lattice contribution to the thermal properties of the fcc metals was calculated from the A4 equation of state, and these results produced a slight improvement over the properties calculated from the A2 equation of state. In order to compare the calculated specific heats and bulk moduli results with experiment~ the electronic contribution to thermal properties was taken into account~ by using the free electron model. We found that the results varied significantly with the value chosen for the number of free electrons per atom.