Síntese e caracterização de complexo tetranuclear de cobre com o ligante resorcinareno

The main objective of the present work is to contribute to the development of the coordination chemistry of macromolecules such as resorcinarene with the synthesis and characterization of new copper complexes with chloride, vanillin and resorcinarene binders, all coordinated to phenanthroline, a biologically active molecule with important properties in biological systems. The complex [(Cu(phen))4(resvan)], was synthesized from the direct reaction of the metals with resorcinarene and generates several possibilities for coordination, which hinders its characterization. Therefore, in order to limit the coordination sites of the ligand, the complex [(Cu(phen))4(resvan)]Cl4 was formed from a new synthetic methodology. The complex cis-[Cu(phen)Cl2], cis-[Cu(phen)(van)]Cl, [(Cu(phen))4(resvan)] and [(Cu(phen))4(resvan)]Cl4 were characterized by spectroscopic techniques such as IR, UV-vis and EPR. By using infrared it has been possible to demonstrate the presence of the phenanthroline ligand in the synthesized complexes, and vanillin in the complex cis- [Cu(phen)(van)]Cl and resvan ligand in the complex [(Cu(phen))4(resvan)], besides this indicating the formation of resorcinarene in the complex [(Cu(phen))4(resvan)]Cl4. The electronic spectra of these coordination compounds indicated the presence of the phenanthroline ligand, by its intense bands in the ultraviolet region. For the complex cis- [Cu(phen)(van)]Cl it still indicated the presence of the ligand vanillin based on intraligand bands of vanillin and charge transfer, LMCT. Furthermore, the spectra showed d-d bands, confirming the formation of metal compounds. The amount of copper atoms present in the complex [(Cu(phen))4(resvan)]Cl4 was estimated from a comparative analysis of the absorbances of solutions of the same concentration of [(Cu(phen))4(resvan)]Cl4 and cis- [Cu(phen)(van)]Cl, which indicates that these compounds have copper atoms in the ratio 4:1. The EPR spectra of the complex cis-[Cu(phen)Cl2], cis-[Cu(phen)(van)]Cl and [(Cu(phen))4(resvan)]Cl4 showed axial profiles, while the complex [(Cu(phen))4(resvan)] showed of axial and rhombic profiles, indicating a change in the symmetry of the Cu (II) to this complex environment. The binders vanillin and resvan underwent biological assays with satisfactory results, both exhibited antioxidant activity and low toxicity, as well vanillin present antitoxoplásmico character.

Contribuições para o processo de verificação de satisfatibilidade módulo teoria em Event-B

Event-B is a formal method for modeling and verification of discrete transition systems. Event-B development yields proof obligations that must be verified (i.e. proved valid) in order to keep the produced models consistent. Satisfiability Modulo Theory solvers are automated theorem provers used to verify the satisfiability of logic formulas considering a background theory (or combination of theories). SMT solvers not only handle large firstorder formulas, but can also generate models and proofs, as well as identify unsatisfiable subsets of hypotheses (unsat-cores). Tool support for Event-B is provided by the Rodin platform: an extensible Eclipse based IDE that combines modeling and proving features. A SMT plug-in for Rodin has been developed intending to integrate alternative, efficient verification techniques to the platform. We implemented a series of complements to the SMT solver plug-in for Rodin, namely improvements to the user interface for when proof obligations are reported as invalid by the plug-in. Additionally, we modified some of the plug-in features, such as support for proof generation and unsat-core extraction, to comply with the SMT-LIB standard for SMT solvers. We undertook tests using applicable proof obligations to demonstrate the new features. The contributions described can potentially affect productivity in a positive manner.

Alquilação de tolueno com propeno, através de complexo ferro (II) ᵦ- diimina homogêneo e heterogeneizado em MCM-41, Al-MCM-41 e SBA-15

This work describes the synthesis and aplication of homogeneous and heterogenized iron catalysts in the alkylation reaction of toluene with propene, empolying experimental design. The homogenous complex was obtained trough the synthesis of the organic ligand folowed by the complexation of the iron(II) chloride. As to the heterogenized complexes, first were synthetized the inorganic supports (SBA-15, MCM-41 and Al-MCM-41). Then, it was synthetized the ligand again, that through funcionalization with chloropropyltrimethoxysilane (CPTMS), was anchored on the support previously calcinated. To these anchored ligands, was complexed the iron(II) chloride, previously solubilizated in tetrahydrofuran (THF). The organic ligand characterization was accomplished trough nuclear magnetic resonance (NMR) and Infrared spectroscopy (IV). The supports were characterized with x-ray diffraction (DRX), texture analysis with nitrogen adsorption/desorption (before and after the anchoring), termogravimetric analysis (TG) and infrared (IV). The metalic content was quantified trough the atomic absorption spectrophotometry (AAS). The complexes were tested in catalytic reactions emolying ethylaluminium sesquichloride (EASC) as co-catalyst in steel reactor, under mecanic stirring. The reaction conditions ranged from 4 to 36 ◦C, with many aluminum/iron ratios. The catalysts were actives in homogeneous and heterogenized ways. The homogenous catalytic complex showed a maximum turnover frequency (TOF) of 8.63 ×103 · h −1 , while, in some conditions, the anchored complexes showed better results, with TOF of until 8.08 ×103 · h −1 . Aditionally, it was possible to determine an equation, to the homogenous catalyst, that describes the product quantity in function of reacional temperature and aluminum/iron ratio.

Efeitos da nicotina no complexo do septo medial na via septo hipocampal em camundongos anestesiados por Ketamina

Nicotine administration in humans and rodents enhances memory and attention, and also has a positive effect in Alzheimer's Disease. The Medial Septum / Diagonal Band of Broca complex (MS/DBB) – a main cholinergic system – massively projects to the hippocampus through the fimbria-fornix, and this pathway is called the septohippocampal pathway. It has been demonstrated that the MS/DBB acts directly on the local field potential (LFP) rhythmic organization of the hippocampus, especially in the rhythmogenesis of Theta (4-8Hz) – an oscillation intrinsically linked to hippocampus mnemonic function. In vitro experiments gave evidence that nicotine applied to the MS/DBB generates a local network Theta rhythm within the MS/DBB. Thus, the present study proposes to elucidate the function of nicotine in the MS/DBB on the septo-hippocampal pathway. In vivo experiments compared the effect of MS/DBB microinfusion of saline (n=5) and nicotine (n=8) on Ketamine/Xylazine anaesthetized mice. We observed power spectrum density in the Gamma range (35 to 55 Hz) increasing in both structures (Wilcoxon Rank-Sum test, p=0.038) but with no change in coherence between these structures in the same range (Wilcoxon Rank-Sum test, p=0.60). There was also a decrease in power of the ketamineinduced Delta oscillation (1 to 3 Hz). We also performed in vitro experiments on the effect of nicotine on membrane voltage and action potential. We patch-clamped 22 neurons in current-clamp mode; 12 neurons were responsive to nicotine, half of them increased firing rate and other 6 decreased, and they significantly differed in action potential threshold (-47.3±0.9 mV vs. -41±1.9 mV, respectively, p=0.007) and halfwidth time (1.6±0.08 ms vs. 2±0.12 ms, respectively, p=0.01). Furthermore, we performed another set of in vitro experiments concerning the connectivity of the three major neuronal populations of MS/DBB that use acetylcholine, GABA or glutamate as neurotransmitter. Paired patch-clamp recordings found that glutamatergic and GABAergic neurons realize intra-septal connections that produce sizable currents in MS/DBB postsynaptic neurons. The probability of connectivity between different neuronal populations gave rise to a MS/DBB topology that was implemented in a realistic model, which corroborates that the network is highly sensitive to the generation of Gamma rhythm. Together, the data available in the full set of experiments suggests that nicotine may act as a cognitive enhancer, by inducing gamma oscillation in the local circuitry of the MS/DBB.

Mapeamento das projeções retinianas para o sistema óptico acessório, colículo superior e complexo pré-tectal do sagui (callithrix jacchus)

The accessory optical system, the pretectal complex, and superior colliculus are important control centers in a variety of eye movement, being extremely necessary for image formation, consequently to visual perception. The accessory optical system is constituted by the nuclei: dorsal terminal nucleus, lateral terminal nucleus, medial terminal nucleus and interstitial nucleus of the posterior superior fasciculus. From a functional point of view they contribute to the image stabilization, participating in the visuomotor activity where all system cells respond to slow eye movements and visual stimuli, which is important for the proper functioning of other visual systems. The pretectal complex comprises a group of nuclei situated in mesodiencephalic transition, they are: anterior pretectal nucleus, posterior pretectal nucleus, medial pretectal nucleus, olivary pretectal nucleus and the nucleus of the optic tract, all retinal projection recipients and functionally are related to the route of the pupillary light reflex and the optokinetic nystagmus. The superior colliculus is an important subcortical visual station formed by layers and has an important functional role in the control of eye movements and head in response to multisensory stimuli. Our aim was to make a mapping of retinal projections that focus on accessory optical system, the nuclei of pretectal complex and the superior colliculus, searching mainly for pretectal complex, better delineation of these structures through the anterograde tracing with the B subunit of cholera toxin (CTb) followed by immunohistochemistry and characterized (measured diameter) synaptic buttons present on the fibers / terminals of the nucleus complex pré-tectal. In our results accessory optical system, including a region which appears to be medial terminal nucleus and superior colliculus, were strongly marked by fibers / terminals immunoreactive CTb as well as pretectal complex in the nucleus: optic tract, olivary pretectal nucleus, anterior pretectal nucleus and posterior pretectal nucleus. According to the characterization of the buttons it was possible to make a better definition of these nucleus.

A compreensão de reação química como um sistema complexo a partir da discussão dos erros e dificuldades de aprendizagem de estudantes do ensino médio

The study of chemical reactions is among the most important contents to the understanding of Chemistry discipline in basic education. However, there are still few studies about chemical reactions as a complex system because, generally, this content is presented in textbooks, taught and even researched in a fragmented form. The thesis here presented aims to investigate, identify and characterize the mistakes and learning difficulties of the students about chemical reactions as a complex system, using for that purpose the analysis of the answers of 126 exams of candidates for the bachelor’s degree in Chemistry Teaching on the entrance exam for the Federal University of Rio Grande do Norte (UFRN). The mistakes and learning difficulties about the parameters ΔG°, Kp, Ea and of the calculation of the amount of substance in a chemical reaction have been identified, as well as the levels of development of the ability to interpret the chemical reaction as a system. The main theoretical source of this study is structured based on the mistakes and learning difficulties (NÚÑEZ, RAMALHO, 2012), of the chemical reactions as complex systems (NÚÑEZ, 1994; RESHETOVA, 1988; SANDERSON, 1968). As methodology, it was prioritized the analysis of the answers to the exams and the interview with the teachers. The results showed typical mistakes in the study of this subject, especially low levels and skill development. No student was able to integrate the different aspects in the systemic understanding of the chemical reaction. From the interviews with Chemistry teachers from High School, it was determined the reasons the teachers assign to those mistakes and learning difficulties. The interviews revealed that the teachers do not work in the perspective of integration of the contents which leads the students to present difficulties and make mistakes related to the content previously mentioned. The study presents a proposal for the organization of the contents of Chemistry discipline for High School as a possibility of a dialectic systemic integration of contents, understanding that this systematic vision, leads to important contributions to the development of the theoretical thinking of the students. We can mention as one of the conclusions of this study, the fact that the non-systemic organization of contents do not favor this kind of thinking in students.

"Do alto da colina" - a província do Rio Grande do Norte, o comércio, os rios Potengi e Jundiaí e o complexo comercial do Guarapes 1850 - 1900

The commercial complex Guarapes was during the second half of the nineteenth century most commercial street of Rio Grande do Norte province. In that time frame, you can see its flourishing as one of the central places of trade in the province in 1850, and its subsequent abandonment in 1900. This thesis aims to investigate, in its first part, the paths that help to understand, as the context of the expansion of global markets in the second half of the nineteenth century enabled the conditions for the emergence of the commercial complex. However, trade relations established in this province through the commercial complex, even participating in this global environment, reserved particular characteristics in their social and trade relations, as if dealing with a peripheral province, we look at the uniqueness of the relationship occurred in this space. In the second part, we seek to understand the importance that the rivers Potengi and Jundiaí had to install the commercial complex Guarapes in the second half of the nineteenth century. As the geographical position in relation to rivers, enabled this space became flow zone and confluence of goods distributed to the various parts of the interior of the province. We also monitor the process that made these rivers leave the role of mobility and transport relations in this space, giving way the railways and roads shooting. In the third part, we seek to understand the commercial complex Guarapes in focus. Analyzing their spatial distribution on the landscape, and how the spatial organization held at the same time traces of the Brazilian patriarchy exposed by Gilberto Freyre, but also "modern" features, due to the increase of a new culture inserted material in the province. We also seek to understand elements of material culture that was the environment of the complex, and how these materials are important sources for understanding this society under study. We treat from the biggest to the smallest fragments without hierarchize them. Understanding that, the study associated the written sources and materials provide a gain in understanding of everyday these people who lived in that area of the complex in the second half of the nineteenth century.

Projeto do complexo ambulatorial do Hospital Universitário João de Barros Barreto visando a critérios de sustentabilidade

The purpose of this dissertation is the architectural project of the ambulatory complex of the Federal University of Pará in Belém. It is a health care establishment whose focus is sustainability, energy efficiency and humanization. This design went through the application of architectural concepts, the study of references (theorical and empirical ones), planning, examining the terrain and its conditions and the preliminay design and resulted in a preliminary architecture blueprint. The empirical research is based on the main building of the Hospital Universitário João de Barros Barreto in Belém, Hospital Sarah Kubitschek of Fortaleza (Architect João Filgueiras de Lima - Lelé) and Hospital e Maternity São Luiz of São Paulo (Architect Siegbert Zanettini). Part of the planning is based on the method "Problem Seeking of Pena and Parshal (2001)". During the development process I sought to incorporate sustainability criterias, energy efficiency and humanization. In relation to sustainability the dissertation focuses on the utilization of rainwater for non-potable usage

Diagnóstico ecotoxicológico dos efluentes lançados no complexo estuarino do Jundiaí/Potengi, Natal/RN

Untreated effluents that reach surface water affect the aquatic life and humans. This study aimed to evaluate the wastewater s toxicity (municipal, industrial and shrimp pond effluents) released in the Estuarine Complex of Jundiaí- Potengi, Natal/RN, through chronic quantitative e qualitative toxicity tests using the test organism Mysidopsis Juniae, CRUSTACEA, MYSIDACEA (Silva, 1979). For this, a new methodology for viewing chronic effects on organisms of M. juniae was used (only renewal), based on another existing methodology to another testorganism very similar to M. Juniae, the M. Bahia (daily renewal).Toxicity tests 7 days duration were used for detecting effects on the survival and fecundity in M. juniae. Lethal Concentration 50% (LC50%) was determined by the Trimmed Spearman-Karber; Inhibition Concentration 50% (IC50%) in fecundity was determined by Linear Interpolation. ANOVA (One Way) tests (p = 0.05) were used to determinate the No Observed Effect Concentration (NOEC) and Low Observed Effect Concentration (LOEC). Effluents flows were measured and the toxic load of the effluents was estimated. Multivariate analysis - Principal Component Analysis (PCA) and Correspondence Analysis (CA) - identified the physic-chemical parameters better explain the patterns of toxicity found in survival and fecundity of M. juniae. We verified the feasibility of applying the only renewal system in chronic tests with M. Juniae. Most efluentes proved toxic on the survival and fecundity of M. Juniae, except for some shrimp pond effluents. The most toxic effluent was ETE Lagoa Aerada (LC50, 6.24%; IC50, 4.82%), ETE Quintas (LC50, 5.85%), Giselda Trigueiro Hospital (LC50, 2.05%), CLAN (LC50, 2.14%) and COTEMINAS (LC50, IC50 and 38.51%, 6.94%). The greatest toxic load was originated from ETE inefficient high flow effluents, textile effluents and CLAN. The organic load was related to the toxic effects of wastewater and hospital effluents in survival of M. Juniae, as well as heavy metals, total residual chlorine and phenols. In industrial effluents was found relationship between toxicity and organic load, phenols, oils and greases and benzene. The effects on fertility were related, in turn, with chlorine and heavy metals. Toxicity tests using other organisms of different trophic levels, as well as analysis of sediment toxicity are recommended to confirm the patterns found with M. Juniae. However, the results indicate the necessity for implementation and improvement of sewage treatment systems affluent to the Potengi s estuary

Projeto raia de fogo: aspectos populacionais da raia de fogo (Dasyatis marianae Gomes, Rosa & Gadig, 2000) e pesca de elasmobrânquios no complexo recifal do Parracho de Maracajaú

The species Dasyatis marianae inhabits coastal areas associated with coral reefs, considered endemic to the northeast of Brazil, occurring from the State of Maranhão to the south of Bahia. Specimens of this species are commonly sighted by divers and fishermen in the area of Maracajaú reefs, a complex reef that is part of the Environmental Protection Area of Coral Reefs (EPACR), which was developed in this study about the ecology and biology of the D. marianae, in order to characterize aspects of population structure in the area of the reef complex of Parracho de Maracajaú. We analyzed 120 specimens caught by artisanal fishing site of the size, weight, sex, stage of maturity and stomach contents. Most subjects were adult males (1.7:1) and was more abundant for rays with lengths between 25 and 29cm of LD, where females reach larger sizes, a feature common to other rays. The largest specimens were captured in the area of seagrass, which is preferred for the species. The distribution of species in the area showed an ontogenetic and sexual segregation, where the youthful occur near the beach, which is a likely area for nursery and growth of the adult females prevail in the seagrass, which apparently has a high prey availability, and Adult males are more distant, a higher proportion occurring in outlying areas, suggesting a habit more exploratory than the females. The evaluation of the reproductive system indicated 3 reproductive cycles per year, one young per pregnancy, and showed that the mature males were smaller than females. The cubs of D. marianae size at birth 12 to 15cm LD. As for diet, the species was characterized as carnivorous crustacean specialist. The performance of visual censuses in different localities allowed to evaluate the density of D. marianae in different environments of the complex. The species occurs in greater numbers in seagrass, environment very important for the conservation of the species. 100 individuals of D. marianae marked in reef complex area enrolled in a recapture rate of 3%. Some behavioral aspects were evaluated, as diurnal pattern of activity, interaction with cleaning and fish Pomacanthus paru followers as Lutjanus analis and Carangoides bartholomaei. Overall, much of the information obtained should be used for management of the species

Implementação de um Módulo de Supervisão para um Sistema de Detecção de Vazamentos em Dutos de Petróleo

The transport of fluids through pipes is used in the oil industry, being the pipelines an important link in the logistics flow of fluids. However, the pipelines suffer deterioration in their walls caused by several factors which may cause loss of fluids to the environment, justifying the investment in techniques and methods of leak detection to minimize fluid loss and environmental damage. This work presents the development of a supervisory module in order to inform to the operator the leakage in the pipeline monitored in the shortest time possible, in order that the operator log procedure that entails the end of the leak. This module is a component of a system designed to detect leaks in oil pipelines using sonic technology, wavelets and neural networks. The plant used in the development and testing of the module presented here was the system of tanks of LAMP, and its LAN, as monitoring network. The proposal consists of, basically, two stages. Initially, assess the performance of the communication infrastructure of the supervisory module. Later, simulate leaks so that the DSP sends information to the supervisory performs the calculation of the location of leaks and indicate to which sensor the leak is closer, and using the system of tanks of LAMP, capture the pressure in the pipeline monitored by piezoresistive sensors, this information being processed by the DSP and sent to the supervisory to be presented to the user in real time