RCAAP Repository

This dissertation presents the results of Raman scattering in crystals of DL-aspartic acid under various temperature conditions. The DL-aspartic acid (C4H7NO4) crystallizes in space group C2h 6 with eight molecules per unit cell, so there are 128 atoms in the unit cell that give rise to 384 normal modes of vibration. Of these modes a total of 192 modes are Raman active, which could be observed in not polarized spectra, but by various factors only some of these modes are observed. We did an attempt identification of all normal modes of vibration that appears in the spectral range between 50 and 3200cm-1 and a study with variation in temperature between 10 and 433 K. The interval between 0 and 150 cm-1 is extremely important for detection of phase transitions because it contains the structural modes of vibration of the lattice. In the case of DL-aspartic acid there was a reversal of intensity for the modes at 82 and 87 cm-1, in considering the extremes of temperature interval measured. This reversal was interpreted as a small conformational change, not associated with a phase transition. With exception of this reversal there were not anomalies, not appearance or disappearance of modes in this region, which pointed to the stability of the material. Another event occurred in this region: the bands at 116 and 132 cm-1, very different at very low temperatures (< 150 K) become indistinguishable at 200 K. This fact can not be associated with a phase transition because the broadening of bands, arising from increasing temperatures, implies the superposition of modes. Added to this there is the fact that the torsional vibrations of the NH3 + and rocking of CO2 - (modes associated with hydrogen bonds) behaved linearly in frequency-temperature curves. Finally we did a study of differential scanning calorimetry, which confirmed what had been observed by Raman spectroscopy - the stability of the structure throughout the temperature range investigated.

A simple mechanism is used in some universities in Brazil to select students at entry and allocate them into various majors. Students rst choose a major and then take exams that either select them in the chosen major or select them out. The matching literature analyzing the student placement issue, points out that this mechanism is not fair and is strategic. Pairs of major & students can be made better o¤ and students tend to disguise their preferences. We build up a dynamic model of choice of major and of grading as well as e¤ort exerted to be successful where preferences are carefully modelled. We estimate this model by simulated using cross-section data about entry exams at Universidade Federal do Ceara in Brazil in 2004. Using the empirical results of the model estimation, we then evaluate changes in the way choices are given to the prospective students. Ex-ante expected utilitarian social welfare indeed increases but it hides very strong distributive e¤ects among students. Strategic e¤ects are found to be very strong.

A pesca de lagostas foi avaliada quanto aos ciclos históricos de produção, produtividade do substrato de algas calcárias como habitat das lagostas Lanulirus argus e Panulirus laevicauda, e sua capacidade de carga e produção instantânea. O material de análise consistiu da série histórica de dados sobre produção, esforço de pesca e CPUE, no Estado do Ceará, de 1974 a 1995. A atividade pesqueira passou por quatro fases: Desenvolvimento, Aceleração, Estabilização e Depleção e, atualmente, se encontra nesta última, caracterizada por (a) tendência de decréscimo da produção, elevadas taxas positivas de crescimento do esforço (b= 1.814 e G=4,1%/ano) e taxas negativas de crescimento da CPUE (b= -0,0387 e G= -3,7%/ano). O Estado do Ceará constitui-se no maior produtor e exportador de lagostas do Brasil, em função de características ambientais muito favoráveis ao crescimento e sobrevivência das lagostas. A plataforma continental, com 48,1% de cobertura pelo substrato de algas calcárias com uma área superficial de 23.088 Km2 (27,6% do total), contém 43,5% da capacidade de carga (7,301.335 kg) e 42,9% da produção instantânea de bimassa (7.398.883 kg), com densidade de 316,3kg/km2. As espécies P. argus e P. laevicauda participam da capacidade de carga com 68,9% e 31,1%, sendo a primeira mais abundante em áreas mais afastadas da costa, a partir da isóbata de 30 m. A capturabilidade é de 55,6% e a intensidade de pesca e densidade ótimas são 5,1 covos/ha e 9,1 ind./ha.

The fluids displacement in porous media has been subject in researches with great scientific and technologic interesting due to its close connection to industry applications, like oil recovery problem, groundwater studies etc. In this thesis, we have investigated through numerical simulations three two-phase flow problems. The first one, is about the secondary oil recovery method, which consist to push the oil using the injection of water; the second case, treats of the tertiary oil recovery method, where the oil viscosity is decreased by the increasing of the temperature; and the last one, is an interfacial hardness model to simulate the glue penetration in porous media. In the first part, we study the behavior of the oil production rate in an isothermal and two-dimensional reservoir field. Water is pushed from an injection to a production well, separated by a distance r. This corresponds to the secondary recovery method in oil reservoirs. We then investigate through direct numerical calculation using the commercial reservoir field simulator STARS of CMG (Computer Modelling Group) the influence of the viscosity ratio (m = moil/mwater) on the oil production (C(t)) when m ≥ 1. We keep m constant through simulation. We first consider a macroscopically disordered and homogeneous reservoir. In this case, all the geometry is accessible to the fluids, but the porosity varies randomly in space. The results show two power law regimes in the oil production curves, with exponent -1/3 and -5/2. We also study the behavior of inhomogeneous system with a percolation-like reservoir geometry. We see in this case a power law behavior with exponent -0.8 in C(t) curves. We verify that the breakthrough time carries units of r 1.8 m1/4 in the homogeneous case and r m1/5 in the inhomogeneous one. When the kind of oil is heavy, tertiaries methods are necessary to improve the recovery. One of the most used techniques is the Steam Injection, where a hot fluid (usually, water or steam) is injected into the reservoir to decrease the oil viscosity. In order to make those studies we consider a microscopic approximation of the medium. The oil viscosity is dependent on temperature according the following function, exp(B/T), where B is a physico-chemical parameter which define the kind of oil, and T is the temperature. A gradient of temperature, ∆T, is applied crossing the medium in the same direction of the injection. Initially, the porous medium is saturated with oil and, then, another fluid is injected. We have considered two cases of injection. The first one, the viscosity of the invading fluid is constant (the viscosity ratio is, then, finite) and the second one, the invading fluid is inviscid (infinite viscosity ratio). Our results show that the recovery efficiency of the oil can increase substantially with the ∆T. We show, also, that the percentage of the oil recovery decreases with B for the finite viscosity ratio case, but the opposite behavior for the other case. In the last part, we propose an Invasion Percolation modified model to simulate the penetration of a fluid into another with hardening interface. Initially, the capillary pressure of each site in the lattice is randomly chosen between 0 and 1, and then, the hardness effect by contact with the defending phase is obtained by increasing the pressure of those sites at interface. The most time exposition a site has the greatest is its pressure value. During this exposition, if a site has pressure greater or equal to 1, that site becomes a pine and cannot be invaded anymore. That represents a glue penetrating into a porous medium where it becomes hard due to exposition with the air. We also consider three different regimes of the displacement according the Bond number, Bo > 0, Bo = 0 and Bo < 0. We have analyzed the influence of that hardness effect in those regimes. We see that, besides the patterns change with this effect, the average behavior do not affect much.

Poucos são os estudos taxonômicos ou morfológicos dos ossos tímpano-perióticos, que constituem o ouvido médio e interno dos cetáces. O presente trabalho tem como objetivo identificar e descrever, numa análise comparativa, as estruturas que formam os osso tímpano-perióticos de seis espécies de pequenos cetáceos que ocorrem na costa no Estado do Ceará, Brasil. Durante o período de janeiro de 1992 a julho de 1996, foram estudados 22 ossos tímpano-perióticos de seis espécies: 15 de Sotalia fluviatilis, 2 de Steno bredanensis, 1 de Stenella clymene, 2 de Tursiops truncatus, 1 de Peponocephala electra e 1 de Ziphius cavirostris. As bulas auditivas foram codificadas e medidas com precisão de 0,05 mm, observando-se 22 características. Também realizou-se, em S. fluviatilis, estudo de simetria bilateral através da comparação das medidas das bulas direita e esquerda, utilizando-se o teste multivariado Hotelling's T2. Não foi observada variação significativa na simetria dos ossos tímpano-perióticos para S. fluviatilis. As relações filogenéticas obtidas pela análise de agrupamento realizada com base nas medidas dos ossos tímpano-perióticos das seis espécies estudadas estão de acordo com árvores filogenéticas obtidas através de análises estatísticas baseadas em seqüências do DNA mitocondrial.

Este trabalho trata do emprego do método de titulação biológica na detecção de toxinas PSP (paralytic shellfish poisopning) em moluscos bivalves ocorrentes no Estado do Ceará (Brasil). Foram preparados extratos musculares de quatro espécies de moluscos: itã= Iphigenia brasiliana; unha-de-velho= Tagellus plebeus; picholeta (fam. unionidae); e sururu= Mytella guyanesis. Os extratos foram inoculados por via intraperitoneal em ratos de laboratório (Musmusculus). As cobaias apresentaram elevadas taxas de sobrevivência.

A morfologia do sistema reprodutivo, o desenvolvimento larval, o período de reprodução e a ooteca de Neritina virginea (Linnaeus, 1758) foram estudadas a partir de material coletado no estuário do Rio Cocó, Estado do Ceará, Nordeste do Brasil. O sistema reprodutor da fêmea de N. virginea tem dois gonóporos; o poro vaginal e o poro para a saída da ooteca. A ooteca tem em média 45 ovos, formato circular e geralmente é coberta com grãos de areia. N. virginea tem desenvolvimento intracapsular que leva em média 288 horas. A atividade reprodutiva ocorre durante os meses de julho a dezembro, que corresponde ao período de estiagem na região. Dados de campo e de laboratório são comparados.

The objective of this study is to analyze the main determinants of reservation wages and unemployment duration using as empirical evidence the PPV - Pesquisa de Padrão de Vida from IBGE (1996-1997). For this purpose, two econometric methodologies are used. For reservation wages, we estimate a traditional wage regression model whose main determinant used was unemployment duration. In order to attenuate simultaneity bias, two-stage regressions are used. The results show that unemployment duration negatively affects the workers’ reservation wages. This corroborates international evidence. Regarding the analysis of duration, we estimate proportional hazards models, with and without unobserved heterogeneity. The estimated parameters have the usual signals, except for the dummy for sex. The risk of leaving unemployment raises initially, and then, after including unobserved heterogeneity, shows a non-monotonic profile. These results offer a new perspective to try to understand the changes that have occurred in the Brazilian labor market during the 90’s.

This paper deals with the estimation of conditional quantiles of linear truncated regression models with known truncation point. The truncated quantile model is shown to posses an important property related to or 2 (0, 1), a set of quantiles of the original latent model: truncation-invariance. Truncation-invariance means that there is a one-to-one function F : or ! tr, tr 2 (0, 1) and where tr is a set of quantiles of the truncated variable. That property turns out to be fundamental to identification of the model, as well as estimation and inference. In fact, simplicity is a major appeal of our semi-parametric approach compared to alternatives estimator of truncated models, as it does not require any modification of available software.

XAVIER, Elódia. Clarice Lispector: a família no banco dos réus. Revista de Letras, Fortaleza, v. 1-2, n.29, p. 51-55, 2008.

This work describes the development and study of environmental friendly epoxies anticorrosives paints, which were formulated using zinc phosphate (ZP), zinc molybdate (ZM), zinc and calcium molybdate (ZCM), zinc phosphomolybdate (ZMP) and zinc and calcium phosphomolybdate (MZAP), as safe alternative to more traditional anticorrosive pigments (lead, chromium and other heavy metals). Additionally, environmental considerations are limiting the use of solvent-borne paints because it contibutes to atmospheric pollution and empairs health problems. Thus, hydrosoluble epoxy resin was used in the formulation of the water-borne paints. The aim od this research is to employ molybdate-based pigments in order to check their efficiency in water borne paints. Inhibitive properties of the pigments were evaluated by potentiodynamic polarization curves, open ciricuit potential (Eoc) and mass loss monitoring during 30 days in immersion test of SAE 1010 steel in aqueous saturated pigment solutions with 10-2 mol dm-3 NaCl. The physical chemical characterization of the corrosion products was carried out by scanning electron microscopy, energy dispersive X-ray and X-ray diffraction techniques. All the tests showed that the phosphomolybdate pigments presented the better corrosion inhibiting properties. All the paints were formulated with 16% (v/v) epoxy resin, 7.5 % (v/v) anticorrosive pigment, and additives and fillers in order to maintain the PVC/CPVC ration equal to 0.8. the dry thickness of the painted samples was approximately 120 μm. The paint performance was monitored by electrochemical impedance spectroscopy (EIS) during immersion tests, of the atmospheric exposition and accelerated ensay of salt spray. The thermal stability of the paintings was also studied by thermal gravimetry and differential scanning calorimetry. The impedance diagrams of all painted samples showed only one capacitive loop, with impedance values higher than 109 Ωcm2. Capacitance values varied between 10-6 and 10-10 Fcm-2. The results suggest that the combination of the molybdate and phosphate gives the best inhibitive properties. About the thermal analyses were observed that the molybdates and phosphomolybdates pigments showed the better performances thus in the thermal stability of epoxy resin, because theses pigments showed higher interaction between pigment-resin; just as in the relation the energy involved in the cure process of polymeric film, because these pigments contribued to reduce the heat involved in the cure process

MARTINS, Gilberto Figueiredo. De profundis- experiências do litoral (presença do espaço arquétipo no romance Perto do coração selvagem, de Clarice Lispector). Revista de Letras, Fortaleza, v. 1-2, n. 29, p. 67-78, 2007-2008.

In the present work, a new route was developed for preparing the compound trans-[Fe(cyclam)(NO+)Cl]Cl2, where the nitric oxide is bonding of the iron in the form linear (NO+) with a bond angle Fe-NO at 177,40. The complex was characterized by uv-visible, infrared and electronic paramagnetic resonances spectroscopies, electrochemical techniques and crystal structure determination were undertaken. The study of the photochemical behavior this nitrosyl complex showed the nitric oxide release and appearance of trans-[Fe(cyclam)(H2O)2]3+ species where the compound is irradiated in the λirr=330 nm in aqueous solution pH=3,4. However, when the compound was irradiated in aqueous solution pH=7,04, was observed the reaction of photoreduction and the production of specie trans-[Fe(cyclam)(NO0)Cl]+ (φ=0,4±0,05 mol/einstein). The study of the photochemical behavior of the trans-[Ru(NH3)4L(NO)]Cl3 complexes, where L=ImK2, BzImK2, Caf and Teo showed the nitric oxide production and appearance of trans-[Ru(NH3)4L(Cl)]2+ species, as product of the photolysis in KCl aqueous solution, in the 330-440 nm region when L= ImK2, Caf and Teo and in the λirr=330 nm when L=BzImK2 . The quantum yields (φNO) for this reaction is sensitive to the nature of L, λirr and pH. The lowest quantum yields are found for L=BzImK2 (φNO=0,005±0,0005 mol/einstein) and the higher was observed for the L=Teo (0,68±0,05 mol/einstein). The absence of observable photochemical reaction when these complexes were irradiated on 410-440nm is explained on basis of the changes in character of the lowest energy MLCT band on function of the ligand L. The incorporation of NO in the composition of many molecules is of interest to study the chemical and enzymatic mechanisms of NO release and the pharmacological aspects and biomedical applications of these compounds. Assuming that the N-nitroso compounds belong to a class of NO donors by transferring nitrosyl homolytically or heterolytically to another species, we have performed the nitrosilation reaction of the cyclam species aiming to study the reactivity of a new N-nitrosamine system toward the release of nitric oxide species. The infrared spectrum of [cyclam(NO)4] displays two characteristic bands at 1454 and 1139 cm-1 assigned to the νNO and νNN modes, respectively. The peaks of νN-H observed in the range 3400-3190 cm-1 in the spectrum of thecyclam starting material disappear in the spectrum of [cyclam(NO)4]. Upon white light photolysis of the compound dispersed in KBr, is observed the decrease of the νNO and νNN and of the appearance of a new band at 2228 cm-1, assigned to the νNO+ stretching mode. This indicates that the [cyclam(NO)4] compound under this photolysis conditions behaves as a nitrosyl donor through an heterolytic cleavage of N-NO bond.

The Petroleum Asphaltic Cement characterized as CAP 50/60, produced at the state of Espírito Santo (Fazenda Alegre), was modified by addition of copolymers of ethylene vinyl acetate (EVA) and EVA from the footwear’s industry residue (EVAR). The original and modified CAPS were characterized by infrared spectroscopy (FTIR) and nuclear magnetic resonance (RMN). Thermal analysis,as thermogravimetry (TG) and differential scanning calorimetry (DSC), was used to evaluate the thermal stability of the samples. The characterization was also performed with empirical tests such as penetration, softening point, elastic recovery and viscosity. The main results indicated that polymer modified CAPS presented larger thermal stability in oxidative atmosphere than in inert atmosphere. The analysis of DSC curves revealed that modified CAPS, when submitted to lower temperatures, were more resistant to the thermal cracks than conventional CAP. Also modified CAPS showed to be more resistant to the thermal oxidative decomposition, when submitted to a simulated aging process. The viscosity of the polymer modified binder was increased in relation to the original binder. Polymer modified CAP EVAR presented non-Newtonian behavior, whereas Newtonian behavior was observed for unmodified CAP. It was observed that modifying the asphalt binder with a copolymer EVAR leads to an improvement in the physical properties in relation to the penetration, softening point, thermal susceptibility and elastic recovery

Two clays of the smectites type, a montmorillonite from the region of Campina Grande (Pb) and the stevensite of Marrocos were used in the process of intercalation and pillarization. Through the results of spectrophotometry of atomic absorption ICP-AES the chemical composition of the montmorillonite was determined as(Na0,43K0,22Ca0,09)(Al1,48,Mg0,18,Fe0,34)2Si4O10(OH)2. By the same process, the composition of the stevensite was determined as (Li0.09Na0.04K0.03Ca0,05)(Al,Mg,Fe)2(Si,Fe,Al)4O10(OH)2. The values of the specific areas were 29 m2.g-1 and 228 m2.g-1, before the intercalation and 106 m2.g-1 and 219 m2.g-1, after the pillarization, for the montmorillonite and stevensite, respectively. The clays were submitted to a treatment for removal of the organic matter and then transformed in the homoionic type with NaCl, and inserted with aluminium complex and pillarization at 500 oC. Through thermogravimetric analysis and X-Ray diffractometry, it was evaluated the influence of the organic matter in the intercalation of the clays. The results showed that the more stable samples were those submitted to treatment with hypochlorate. The stevensite presented catalytic activity of about 15% above the capacity of the montmorillonite, whose maximum was 50% at 315 oC. Its percentage of isomerization however, in the order of 82%, was about 13% more than for stevensite. The production of isomers of the Mono and Di type were similar for the two clays, being of 84% and 16% respectively. The predominant isomers for both clays were 3-methylheptane and 2-4-dimethylhexane. Despite the catalytic activities of the pillared clays having not reached the same levels for zeolites as ZSM-22, the isomerization relative percentages exceeded the figures reported for this zeolite, at the temperature where the activities of these clays are maximum.

This research work describes the synthesis, characterization, reactivity and properties of new complexes of ruthenium with the ligands o-phenylenediamine, oaminophenol, catechol, naphtalenediol, dopamine and adrenaline and the mer-[RuIIICl3(dppb)(H2O)] complex. Also, it describes a new metal-assisted oxidative dehydrogenation of the interaction o-phenylenediamine ligand and the mer- [RuIIICl3(dppb)(H2O)] complex. The mer-[RuIIICl3(dppb)(H2O)] complex has shown to be a versatile compound as starting material. The reaction of this compound with the o-phenylenediamine ligand produced a mixture of compounds with the bqdi and opda forms of the o-phenylene ligand, the trans-[RuIICl2(dppb)(bqdi)] and trans-[RuIICl2(dppb)(opda)] complexes, that it was confirmed for the observation of two singlet signals at d 47 and d 26 in the 31P{1H} NMR spectrum. One very first assignment suggests that the opda ligand is oxidized to bqdi form during the reaction, according to mechanism proposed in this work. However, the product of the reaction between the o-phenylenediamine ligand and the mer-[RuIIICl3(dppb)H2O] complex by the slow addition of the ligand showed only one signal at d 26 in the 31P{1H} NMR spectrum, indicating that the trans-[RuIICl2(dppb)(bqdi)] complex is preferentially produced. This complex was characterized by the elemental analysis, spectroscopic and electrochemical techniques and its structure has been determined by X-ray crystallography. Aiming to reinforce the proposed mechanism, we conducted the reaction of the o-phenylenediamine ligand with the [RuIICl2(dppb)(PPh3)] complex. Since the ruthenium metal center is already in the reduced state, it will not promote any redox change in the ligand. Thus, the complex produced showed only one signal at d 26 in the 31P{1H} NMR spectrum, indicating the formation of the trans-[RuIICl2(dppb)(opda)] complex that it was characterized by the elemental analysis, spectroscopic and electrochemical techniques and its structure has been determined by X-ray crystallography. The compounds isolated of type trans-[RuIICl2(dppb)(X)], X = quinone, dopamine and adrenaline and cis-[RuIICl2(dppb)(L)], L = o-aminophenol in the quinonoide form and bqdi, were characterized by the spectroscopic and electrochemical techniques.

Lung cancer is configured with as a great public health problem in the world. From a rare disease in the past, its incidence has changed in several countries in recent years, which was observed mainly in females. Thus, the research aimed to survey the research developed on the theme, especially the change in the distribution of histological types of lung cancer. A bibliographic study, developed from original articles, review articles, theses and dissertations, journals indexed in Medline, Lilacs, NCBI, Capes, Scielo, BIREME and Pub Med data basis, written in English and Portuguese as well as books written about lung neoplasia, a total of 49 sources surveyed. The results showed that the rates of new cases and mortality are higher in developed countries, especially in the United States of America (USA) and Europe. Although controversial, it is likely that women are more susceptible to lung cancer than men. These gender differences are largely related to smoking. However, both in men and women, the prevention, in other words, the anti-smoking combat, major risk factor of this neoplasia, is a measure of public health priority.

BARBOSA, Vânia Maria Castelo; MORAES, Vera Lucia Albuquerque de. A linguagem de Clarice Lispector como desautomatização da vida. Revista de Letras, Fortaleza, v.1-2, n. 29, p.81-84, 2007-2008.

According to the World Health Organization 42 millions of people aged over 3 years old have some kind of audio loss. In Brazil, there are no data in population level about the importance of hearing loss, but estimates show that 1,5% of the Brazilian population is a bearer of any hearing problem. Hearing alterations are considered by WHO, problems of public health and can, in many cases, be minimized and even be avoided through a primary attention in audiology with the insertion of audio health programs, reducing costs with specialized attendance. About this aspect, the objective of this study was to investigate the knowledge of professionals working at Family Health Care Program of UBASF Cesar Cals about hearing health. Thus, 19 interviews with FHCP (Family Health Care Program) professionals were made in order to define analytical categories to posterior discussion. It’s important to reinforce that the results evidenced lack of knowledge and sensibility of professionals concerning audio loss as one of the main reasons to the non-fulfillment of hearing health promotion. This way, the lack of training or orientation about the issue has also contributed to the non-recognition of hearing loss as a health problem in the area and the non- practicality of its prevention.Thus, we conclude that there is a necessity that the prevention measures of hearing health problems could be adopted, having as a starting point the sensitivity and the training of the FHCP staff.

O acidente do trabalho, ocorrência freqüente na vida do trabalhador, é, desde os primórdios dos tempos, uma preocupação para aqueles que lutam para sobreviver. A presente pesquisa dedicou-se ao estudo dos acidentes do trabalho fatais ocorridos com eletricitários ligados direta ou indiretamente à concessionária de energia elétrica do Estado do Ceará no período de 1998 a 2004. Os dados foram obtidos de 3 fontes. Dispostos em tabelas e analisados obtendo-se como resultado que 33 trabalhadores do setor elétrico, todos do sexo masculino, foram vítimas de acidentes do trabalho fatais; sendo que destes somente 13 haviam sido notificados com tal, a média de idade foi de 33anos; 60% eram casados; 76% tinham filhos; 70% das vítimas fatais eram eletricistas; 48% das vítimas tinham menos de 1 ano de serviço; 15% eram sindicalizados; 82% eram trabalhadores de empresas terceirizadas; 66% das vítimas morreu em decorrência de choque elétrico, sendo a média tensão a mais freqüente; os MMSS e as queimaduras foram os locais e as lesões mais encontradas; o ano de 1999 registrou o maior número de acidentes fatais e 68% aconteceram no horário comercial; 91% dos acidentes aconteceram no Interior do Estado; 83% aconteceram em vias públicas. Encontrou-se 21% de concordância entre as 3 fontes pesquisadas e 52% entre 2 fontes. Concluiu-se a ocorrência de um aumento acentuado do número de acidentes do trabalho fatais no setor elétrico no período de 1998 a 2002, o qual corresponde ao início da privatização da concessionária de energia elétrica do Ceará.