Room Temperature, Metal-Free Synthesis of Diaryl Ethers with Use of Diaryliodonium Salts

A fast, high-yielding synthesis of diaryl ethers with use of mild and metal-free conditions has been developed. The scope includes bulky ortho-substituted diaryl ethers, which are difficult to obtain by metal-catalyzed protocols. Halo-substituents, racemization-prone amino acid derivatives, and heteroaromatics are also tolerated. The methodology is expected to be of high utility in the synthesis of complex molecules and in the pharmaceutical industry.

No tempo dos brotos: juventude e diversão em Petrópolis e no Tirol (1945-1960)

The urban growth of Rio Grande do Norte capital gave his boldest step in the three earlier decades of the twentieth century seeking to catch up with foreign metropolis and also most developed Brazilian cities, for example, Rio de Janeiro. Novelties were such bulky that we can notice the rise of a new city which in many aspects superseded that one considered provincial by local intelligentsia. These urban interferences scratched city ground leaving indelible marks until the present day. The exacerbated growth of the city related to the 1940s, when Natal begins hosting the largest allied military base outside United States in the advent of World War II is important at a time when the city´s population doubled. The emergence of new leisure institutions, amidst already existing ones, continued marking the places as sociabilities and leisure permeated with meanings and representations are revealed. This work sought to know the sociability of Tirol and Petrópolis neighborhoods in Natal, in the period from 1945 to 1960, when the city witnesses the consolidation of a market increasingly focused on leisure and young people start to have a special participation in this process.

A New Impedance Measurement System for PZT-Based Structural Health Monitoring

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estudo teórico QTAIM e DFT dos compostos de coordenação: efeito quelato, titanocenos e ligação química

This work is a study of coordination compounds by quantum theory of atoms in molecules (QTAIM), based on the topological analysis of the electron density of molecular systems, both theoretically and experimentally obtained. The coordination chemistry topics which were studied are the chelate effect, bent titanocene and chemical bond in coordination complexes. The chelate effect was investigated according to topological and thermodynamic parameters. The exchange of monodentate ligands on polydentate ligands from same transition metal increases the stability of the complex both from entropy and enthalpy contributions. In some cases, the latter had a higher contribution to the stability of the complex in comparison with entropy. This enthalpic contribution is explained according to topological analysis of the M-ligand bonds where polidentate complex had higher values of electron density of bond critical point, Laplacian of electron density of bond critical point and delocalization index (number of shared electrons between two atoms). In the second chapter, was studied bent titanocenes with bulky cyclopentadienyl derivative π-ligand. The topological study showed the presence of secondary interactions between the atoms of π-ligands or between atoms of π-ligand and -ligand. It was found that, in the case of titanocenes with small difference in point group symmetry and with bulky ligands, there was an nearly linear relationship between stability and delocalization index involving the ring carbon atoms (Cp) and the titanium. However, the titanocene stability is not only related to the interaction between Ti and C atoms of Cp ring, but secondary interactions also play important role on the stability of voluminous titanocenes. The third chapter deals with the chemical bond in coordination compounds by means of QTAIM. The quantum theory of atoms in molecules so far classifies bonds and chemical interactions in two categories: closed shell interaction (ionic bond, hydrogen bond, van der Waals interaction, etc) and shared interaction (covalent bond). Based on topological parameters such as electron density, Laplacian of electron density, delocalization index, among others, was classified the chemical bond in coordination compounds as an intermediate between closed shell and shared interactions

Síntese e caracterização de zeólita beta hierarquizada e materiais híbridos micro-mesoporosos aplicados no craqueamento de PEAD

A catalyst of great interest to the scientific community tries to unite the structure of ordered pore diameter from mesoporous materials with the properties of stability and acid activity to microporous zeolites. Thus a large number of materials was developed in the past decades, which although being reported as zeolites intrinsically they fail to comply with some relevant characteristics to zeolites, and recently were named zeolitic materials of high accessibility. Among the various synthesis strategies employed, the present research approaches the synthesis methods of crystallization of silanized protozeolitic units and the method of protozeolitic units molded around surfactant micelles, in order for get materials defined as hierarchical zeolites and micro-mesoporous hybrid materials, respectively. As goal BEA/MCM-41 hybrid catalysts with bimodal pore structure formed by nuclei of zeolite Beta and cationic surfactant cetyltrimethylammonium were developed. As also was successfully synthesized the hierarchical Beta zeolite having a secondary porosity, in addition to the typical and uniform zeolite micropores. Both catalysts were applied in reactions of catalytic cracking of high density polyethylene (HDPE), to evaluate its properties in catalytic activity, aiming at the recycling of waste plastics to obtain high value-added raw materials and fuels. The BEA/MCM-41 hybrid materials with 0 days of pre-crystallization did not show enough properties for use in catalytic cracking reactions, but they showed superior catalytic properties compared to those ordered mesoporous materials of Al-MCM-41 type. The structure of Beta zeolite with hierarchical porosity leads the accessibility of HDPE bulky molecules to active centers, due to high external area. And provides higher conversion to hydrocarbons in the gasoline range, especially olefins which have great interest in the petrochemical industry

Modelagem e desenvolvimento de um banco de dados geográficos : aplicação à elaboração de mapas de sensibilidade ambiental ao derramamento de óleo na área costeira entre galinhos e São Bento do Norte-RN

The area between Galinhos and São Bento do Norte beaches, located in the northern coast of the Rio Grande do Norte State is submitted to intense and constant processes of littoral and aeolian transport, causing erosion, alterations in the sediments balance and modifications in the shoreline. Beyond these natural factors, the human interference is huge in the surroundings due to the Guamaré Petroliferous Pole nearby, the greater terrestrial oil producing in Brazil. Before all these characteristics had been organized MAMBMARE and MARPETRO projects with the main objective to execute the geo-environmental monitoring of coastal areas on the northern portion of RN. There is a bulky amount of database from the study area such as geologic and geophysical multitemporal data, hydrodynamic measurements, remote sensing multitemporal images, thematic maps, among others; it is of extreme importance to elaborate a Geographic Database (GD), one of the main components of a Geographic Information System (GIS), to store this amount of information, allowing the access to researchers and users. The first part of this work consisted to elaborate a GD to store the data of the area between Galinhos and São Bento do Norte cities. The main goal was to use the potentiality of the GIS as a tool to support decisions in the environmental monitoring of this region, a valuable target for oil exploration, salt companies and shrimp farms. The collected data was stored as a virtual library to assist men decisions from the results presented as digital thematic maps, tables and reports, useful as source of data in the preventive planning and as guidelines to the future research themes both on regional and local context. The second stage of this work consisted on elaborate the Oil-Spill Environmental Sensitivity Maps. These maps based on the Environmental Sensitivity Index Maps to Oil Spill developed by the Ministry of Environment are cartographic products that supply full information to the decision making, contingency planning and assessment in case of an oil spilling incident in any area. They represent the sensitivity of the areas related to oil spilling, through basic data such as geology, geomorphology, oceanographic, social-economic and biology. Some parameters, as hydrodynamic data, sampling data, coastal type, declivity of the beach face, types of resources in risk (biologic, economic, human or cultural) and the land use of the area are some of the essential information used on the environmental sensitivity maps elaboration. Thus using the available data were possible to develop sensitivity maps of the study area on different dates (June/2000 and December/2000) and to perceive that there was a difference on the sensitivity index generated. The area on December presented more sensible to the oil than the June one because hydrodynamic data (wave and tide energy) allowed a faster natural cleaning on June. The use of the GIS on sensitivity maps showed to be a powerful tool, since it was possible to manipulate geographic data with correctness and to elaborate more accurate maps with a higher level of detail to the study area. This presented an medium index (3 to 4) to the long shore and a high index (10) to the mangrove areas highly vulnerable to oil spill

Malformação arteriovenosa uterina após doença trofoblástica gestacional

OBJETIVO: investigar a presença e resultados de malformações vasculares uterinas (MAVU) após doença trofoblástica gestacional (DTG). MÉTODOS: estudo retrospectivo com inclusão de casos diagnosticados entre 1987 e 2004; 2764 pacientes após DTG foram acompanhadas anualmente com ultra-sonografia transvaginal e Doppler colorido no Centro de Neoplasia Trofoblástica Gestacional da Santa Casa da Misericórdia (Rio de Janeiro, RJ, Brasil). Sete pacientes tiveram diagnóstico final de MAVU baseado em análise ultra-sonográfica - índice de pulsatilidade (IP), índice de resistência (IR) e velocidade sistólica máxima (VSM) - e achados de imagens de ressonância nuclear magnética (RNM). Dosagens negativas de beta-hCG foram decisivas para estabelecer o diagnóstico diferencial com DTG recidivante. RESULTADOS: a incidência de MAVU após DTG foi 0,2% (7/2764). Achados ultra-sonográficos de MAVU: IP médio de 0,44±0,058 (extremos: 0,38-0,52); IR médio de 0,36±0,072 (extremos: 0,29-0,50); VSM média de 64,6±23,99 cm/s (extremos: 37-96). A imagem de RNM revelou útero aumentado, miométrio heterogêneo, espaços vasculares tortuosos e vasos parametriais com ectasia. A apresentação clínica mais comum foi hemorragia transvaginal, presente em 52,7% (4/7) dos casos. Tratamento farmacológico com 150 mg de acetato de medroxiprogesterona foi empregado para controlar a hemorragia, após a estabilização hemodinâmica. Permanecem as pacientes em seguimento, assintomáticas até hoje. Duas pacientes engravidaram com MAVU, com gestações e partos exitosos. CONCLUSÃO: presente sangramento transvaginal em pacientes com beta-hCG negativo e história de DTG, deve-se considerar a possibilidade de MAVU e solicitar avaliação ultra-sonográfica com dopplervelocimetria. O tratamento conservador é a melhor opção na maioria dos casos de MAVU pós-DTG.

Acid phosphatase activity distribution in salivary glands of triatomines (Heteroptera, Reduviidae, Triatominae)

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

Cytochemical characterization of Triatoma infestans and Panstrongylus megistus salivary gland cells (Hemiptera, Reduviidae, Triatominae)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Absolute configuration reassignment of two chromanes from Peperomia obtusifolia (Piperaceae) using VCD and DFT calculations

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

Relationship of venom ontogeny and diet in Bothrops

We studied ontogenetic changes in venom toxicity of the pitvipers Bothrops jararaca and B. alternatus in order to evaluate the relationship between venom action and diet. Toxicity tests (LD50) were performed for the venoms of adult and juvenile snakes on mice and bullfrog froglets, which represented endothermic and ectothermic prey respectively. The venom of juveniles of B. jararaca, but not of B. alternatus, had a higher toxicity on anurans than that of adults. This finding is consistent with the feeding habits of these two species, because juveniles of B. jararaca feed mainly on small anurans and lizards, shifting to endothermic prey at maturity, whereas B. alternatus preys mainly on endotherms throughout its life. Venom toxicity in endotherms was higher for adults of B. jararaca compared to juveniles, a feature not observed for B. alternatus. It is proposed that prey death/immobilization is the main function of the venom of juvenile snakes. As the snake grows, the digestive role of venom may become increasingly important, because adults prey upon large and bulky prey. The importance of adult venoms in prey digestion is reflected in their higher proteolytic activity.

Planejamento urbano e geração de empregos: A cidade de São Paulo (Brasil) nos anos 90

This paper attempts to show the convergence of principles between labor market politics and urban management, emphasizing it relationship with pro-market theories. Limits and possibilities of the application of this theoretical frame were investigated by examining the changes in both composition and stock of labor in three important business spaces in São Paulo: Central Area, Paulista Avenue and the new expansion front near Luiz Carlos Berrini and Águas Epraiadas avenues. Despite the claims of pro-market theoreticians, information provided by Labor Ministry showed that between 1996 and 2000, a re-arrangemenet of the workers contingent among the investigated areas occurred, instead of the expected growth. The favorable behavior registered in Berrini/ Águas Espraiadas, because of the bulky volume of investments, took place at the same time that a decrease of labor in the Downtown; meanwhile, in Paulista, a growth of the number of employees was observed, in spite of the landing less elevated of investments.

Hydatidiform mole resulting from sexual violence

Background. Hydatidiform mole (HM) is characterized by abnormal proliferation of human trophoblast with producers functioning tissues of human chorionic gonadotropin. It can evolve with ovarian cysts tecaluteínicos, hypertension of pregnancy or hyperthyroidism. The incidence of HM is variable and its etiology poorly known, associated with nutritional factors, environmental, age, parity, history of HM, oral contraceptives, smoking, consanguinity or defects in germ cells. There is no reference in literature on HM resulting from sexual violence, objective of this report. Method. Description of two cases of HM among 1146 patients with pregnancy resulting from sexual violence treated at Hospital Pérola Byington, São Paulo, from July 1994 to August 2011. Results. The cases affected young, white, unmarried, low educated and low parity women. Sexual violence was perpetrated by known offenders unrelated to the victims, under death threat. Ultrasound and CT of the pelvis showed bulky uterus compatible with HM without myometrial invasion. One case was associated with theca lutein cysts. The two cases were diagnosed in the second trimester of pregnancy and evolved with hyperthyroidism. There was no hypertension, disease recurrence, metastasis or sexually transmitted infection. Conclusion. The incidence of HM was 1:573 pregnancies resulting from rape, within the range estimated for Latin American countries. Trophoblastic material can be preserved to identify the violence perpetrator, considering only the paternal HM chromosomes. History of sexual violence should be investigated in cases of HM in the first half of adolescence and women in a vulnerable condition. © 2012 Drezzet et al; licensee BioMed Central Ltd.

Centralização e descentralização: mudanças institucionais e seus impactos na economia da província de São Paulo (1835-1850)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Hidrólise de cana-de-açúcar com cal virgem e cal hidratada micropulverizadas na alimentação de vacas leiteiras

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)