Curtin-Hammett versus non-Curtin-Hammett frameworks is optimizing the enantioselective binolam/titanium(IV)-catalyzed cyanobenzoylation of aldehydes: Part 2

Extensive experimental and computational studies have been carried out on the enantioselective titanium(IV)-catalyzed cyanobenzoylation of aldehydes using 1:n Binolam:Ti(OiPr)4 mixtures as precatalysts, with the purpose of identifying the key mechanistic aspects governing enantioselectivity. HCN and isopropyl benzoate were detected in the reacting mixtures. This, as well as the reaction’s response to the presence of an exogenous base, and the failure to react in the presence of Binol:Ti(OiPr)4 mixtures, led us to propose not a direct cyanobenzoylation but an indirect process involving enantioselective hydrocyanation followed by O-benzoylation. Computational work provided positive evidence for the intervention of both indirect and direct cyanobenzoylation routes, the former being faster. However, the standard Curtin–Hammett-based optimization search ended with unsatisfactory results. Experimental and computational DFT studies (B3LYP/6-31G*) led us to conclude that: (1) the overall cyanobenzoylation of aldehydes catalyzed by 1:n Binolam:Ti(OiPr)4 mixtures involves an enantioselective hydrocyanation followed by an stereochemically inert O-benzoylation; (2) the initial complexes prevailing in a 1:1 Binolam:Ti(OiPr)4 mixture are the solvated mononuclear monomer 5·2(iPrOH) and solvated dinuclear dimer 9·2(iPrOH), whereas 9·2(iPrOH) is the major component in a 1:2 or higher 1:n mixture; (3) since the slowest step is that of benzoylation of ligated iPrOH which yields the actual catalysts 5–9, the catalytic system fits into a non-Curtin–Hammett framework, the final products deriving from a kinetic quench of the competing routes; and (4) accordingly, catalysis by 1:1 Binolam:Ti(OiPr)4 mixtures should involve cyanobenzoylations promoted by mononuclear 5, contaminated with those promoted by some dinuclear open dimer 9, whereas cyanobenzoylations catalyzed by a 1:2 and higher 1:n mixtures should be the result of catalysis promoted by the large amounts of dinuclear open dimer 9.

Isoprene-mediated lithiation of imidazole derivatives: mechanism considerations

The isoprene-mediated lithiation, with lithium metal, of different imidazole derivatives is an interesting methodology for their functionalization. Studies of different possible intermediates involved in the reaction employing density functional theory calculations, at the B3LYP/6-311++G(d,p) level are considered. A plausible mechanism is described, in which isoprene is reduced, to the corresponding radical anion, in the presence of Li(s), acting then as a base deprotonating N-methylimidazole (NMI) and producing the 1,1-dimethylallyl radical. This radical is further reduced by the excess of lithium proceeding once more as a base. This final step produces stable final products that compensate the previous equilibriums, making favourable the whole process.

Uso do zoneamento ambiental do Médio Rio Grande na sub-bacia hidrográfica do Ribeirão Bocaina - Passos/MG

Este trabalho é parte integrante do Projeto Grande Minas - União pelas Águas, que realizou o Zoneamento Ambiental das Sub-bacias Hidrográficas dos Afluentes Mineiros do Médio Rio Grande. Após a obtenção dos produtos finais do zoneamento, entra-se agora, na fase de “Implementação”, ou seja, de sua aplicação direta para contribuir no processo de gestão dos recursos hídricos das sub-bacias hidrográficas da área de estudo. Neste trabalho estuda-se, especificamente, a sub-bacia hidrográfica do Ribeirão Bocaina, considerada uma das 34 sub-bacias que envolvem a Bacia Hidrográfica dos Afluentes Mineiros do Médio Rio Grande e situa-se no município de Passos-MG, possuindo uma área de 457,9 km². O trabalho busca dar uma contribuição para a gestão dos recursos hídricos nesta sub-bacia, que vem sofrendo com a degradação do seu recurso hídrico. O objetivo é disponibilizar instrumentos cartográficos para subsidiar a gestão dos recursos hídricos e, com isto, contribuir com a sua preservação e uso sustentável. A sistemática metodológica envolve uma análise dos aspectos legais da área de estudo; a construção de um Banco de Dados Digital georreferenciado com informações sobre os meios físico, biótico e socioeconômico da sub-bacia e a produção de uma carta derivada, de cunho interpretativo e de fácil leitura, que possa ser utilizada diretamente pelo gestor público nas tomadas de decisões. A base digital produzida conta com uma série de mapas digitais, dentre eles: mapas climáticos, de solos, declividades, geomorfológico, geológico, de sistemas aquíferos, hidrográfico, uso e ocupação do solo. Com relação à carta derivada, destaca os terrenos que apresentam maior predisposição à alterações diretas nos recursos hídricos.

Optimization of co-current spray drying process of sugar-rich foods. Part I - Moisture and glass transition temperature profile during drying

A steady state mathematical model for co-current spray drying was developed for sugar-rich foods with the application of the glass transition temperature concept. Maltodextrin-sucrose solution was used as a sugar-rich food model. The model included mass, heat and momentum balances for a single droplet drying as well as temperature and humidity profile of the drying medium. A log-normal volume distribution of the droplets was generated at the exit of the rotary atomizer. This generation created a certain number of bins to form a system of non-linear first-order differential equations as a function of the axial distance of the drying chamber. The model was used to calculate the changes of droplet diameter, density, temperature, moisture content and velocity in association with the change of air properties along the axial distance. The difference between the outlet air temperature and the glass transition temperature of the final products (AT) was considered as an indicator of stickiness of the particles in spray drying process. The calculated and experimental AT values were close, indicating successful validation of the model. (c) 2004 Elsevier Ltd. All rights reserved.

The effect of complexes on combustion

The twin goals of low and efficient fuel use and minimum emissions are increasingly being addressed by research in both the motor and the catalyst industries of the world. This study was designed to attempt to investigate these goals. For diesel engine vehicles, this can be achieved by improving the efficiency of the fuel combustion in the combustion chamber. By having a suitable oxidation catalyst in the fuel one would expect the efficiency of the fuel combustion to be increased and fewer partial oxidation products to be formed. Also by placing a catalyst converter in the exhaust system partial oxidation products may be converted to more desirable final products. Finally, in this research the net catalytic effect of using an additive treated fuel and a blank ceramic monolith to trap the metal in the exhaust gases for potential use as catalytic converter was investigated. Suitable metal additives must yield a stable solution in the fuel tank. That is, they should not react with the air, water and rust that are always present. The research was targeted on the synthesis of hydrocarbon-soluble complexes that might exhibit unusually slow rates of ligand substitution. For materials containing metal ions, these properties are best met by using multi-dentate ligands that form neutral complexes. Metal complexes have been synthesised using acetylacetone derivatives, schiff base ligands and macrocyclic polyamine ligands, as potential pro-oxidant additives. Their thermal stabilities were also investigated using a differential thermal analysis instrument. The complexes were then investigated as potential additives for use in diesel fuel. The tests were conducted under controlled conditions using a diesel combustion bomb simulating the combustion process in the D.I. diesel engine, a test bed engine, and a vehicle engine.

The creep behaviour of pressure diecast zinc-aluminium based alloys

The creep behaviour of three pressure diecast commercial zinc-aluminium based alloys: Mazak 3, corresponding to BS 1004A, and the new alloys ZA.8 and ZA.27 with a series of alloys with compositions ranging from 0% to 30% aluminium was investigated. The total creep elongation of commercial alloys was shown to be well correlated using an empirical equation. Based on this a parametrical relationship was derived which allowed the total creep extension to be related to the applied stress, the temperature and the time of test, so that a quantitative assessment of creep of the alloys could be made under different conditions. Deviation from the normal creep kinetics occurred in alloys ZA.8 and ZA.27 at very low stresses, 150°C, due to structural coarsening combined with partial transformation of ε -phase into T' phase. The extent of primary creep was found to increase with aluminium content, but secondary creep rates decreased in the order Mazak 3, ZA.8 and ZA.27. Thus, based on the above equation, ZA.8 was found to have a substantially better total creep resistance than ZA.27, which in turn was marginally better than Mazak 3 for strains higher than 0.5%, but inferior for smaller strains, due to its higher primary creep extension. The superior creep resistance of ZA.8 was found to be due to the presence of strictly-orientated, thin plate-like precipitates of ε(CuZn4) phase in the zinc matrix of the eutectic and the lamellarly decomposed β phase, in which the precipitation morphology and orientation of ε in the zinc matrix was determined. Over broad ranges of temperature and stresses, the stress exponents and activation energies for creep were found to be consistent with some proposed creep rate mechanisms; i.e. viscous glide for Mazak 3, dislocation climb over second phase particles for ZA.8 and dislocation climb for ZA.27, controlled by diffusion in the zinc-rich phase. The morphology of aluminium and copper-rich precipitates formed from the solid solution of zinc was clearly revealed. The former were found to further increase the creep rate of inherently low creep resistant zinc, but the latter contributed significantly to the creep resistance. Excess copper in the composition, however, was not beneficial in improving the creep resistance. Decomposition of β in copper-containing alloys was found to be through a metastable Zn-Al phase which is strongly stabilised by copper, and the final products of the decomposition had a profound effect on the creep strength of the alloys. The poor creep resistance of alloy ZA.27 was due to the presence of particulate products derived from decomposed β-phase and a large volume of fine, equiaxed products of continuously decomposed α-dendrites.

Ontology-based pathways generation for biomass to bioenergy conversion

Bio energy is a renewable energy and a solution to the depleting fossil fuels. Bio energy such as heat, power and bio fuel is generated by conversion technologies using biomass for example domestic waste, root crops, forest residue and animal slurry. Pyrolysis, anaerobic digestion and combined heat and power engine are some examples of the technologies. Depending on the nature of a biomass, it can be treated with various technologies giving out some products, which can be further treated with other technologies and eventually converted into the final products as bio energy. The pathway followed by the biomass, technologies, intermediate products and bio energy in the conversion process is referred to as bio energy pathway. Identification of appropriate pathways optimizes the conversion process. Although there are various approaches to create or generate the pathways, there is still a need for a semantic approach to generate the pathways, which allow checking the consistency of the knowledge, and to share and extend the knowledge efficiently. This paper presents an ontology-based approach to automatic generation of the pathways for biomass to bio energy conversion, which exploits the definition and hierarchical structure of the biomass and technologies, their relationship and associated properties, and infers appropriate pathways. A case study has been carried out in a real-life scenario, the bio energy project for the North West of Europe (Bioen NW), which showed promising results.

Guest editorial

Full text: With the rapid development of the aerospace industry, manufacturing technologies have to continuously develop and adjust themselves to ever-growing demands coming from more complex component designs and the use of highly engineered materials. Today there is an increased number of manufacturers contributing to the realization of final products, i.e. avionics, so it is easy to perceive the truly globalized dimension of the aerospace manufacturing business. With this comes the demand for further engineering developments on which the academic/industrial research institutes need to deliver solutions to real aerospace manufacturing problems. This is a challenging task since aerospace manufacturing technologies have to cover a wide range of materials (from composites to advanced Ni/Ti alloys), processes (from forging to non-traditional machining and assembly), and parts’ dimensions/batch sizes (from airframes to turbine blades). In this wide context, this Special Issue includes high quality theoretical and experimental scientific contributions on the following topics related to the aerospace manufacturing technology: (a) machining of advance aerospace alloys; (b) abrasive processes applied to aerospace components; (c) surface treatments to enhance fatigue performance of aerospace components; (d) joining and assembly of aerospace components; (e) laser machining of aerospace alloys; (f) automated/supervised manufacture of aerospace components; (g) quality supervision of aerospace manufacturing routes. The breadth of topics in this Special Issue is perhaps indicative of the complexity and challenges that the research related to aerospace manufacturing technology can offer. We hope that this issue will act as a catalyst for the development of further research, academic and industrial interactions, and publications related to aerospace manufacturing technologies for the benefit of the academic and industrial research communities.

Speciation, metabolism, toxicity, and protein-binding of different arsenic species in human cells

Despite of its known toxicity and potential to cause cancer, arsenic has been proven to be a very important tool for the treatment of various refractory neoplasms. One of the promising arsenic-containing chemotherapeutic agents in clinical trials is Darinaparsin (dimethylarsinous glutathione, DMA III(GS)). In order to understand its toxicity and therapeutic efficacy, the metabolism of Darinaparsin in human cancer cells was evaluated. With the aim of detecting all potential intermediates and final products of the biotransformation of Darinaparsin and other arsenicals, an analytical method employing high performance liquid chromatography inductively coupled mass spectrometry (HPLC-ICP-MS) was developed. This method was shown to be capable of separating and detecting fourteen human arsenic metabolites in one chromatographic run. The developed analytical technique was used to evaluate the metabolism of Darinaparsin in human cancer cells. The major metabolites of Darinaparsin were identified as dimethylarsinic acid (DMAV), DMA III(GS), and dimethylarsinothioyl glutathione (DMMTAV(GS)). Moreover, the method was employed to study the conditions and mechanisms of formation of thiol-containing arsenic metabolites from DMAIII(GS) and DMAV as the mechanisms of formation of these important As species were unknown. The arsenic sulfur compounds studied included but were not limited to the newly discovered human arsenic metabolite DMMTA V(GS) and the unusually highly toxic dimethylmonothioarsinic acid (DMMTAV). It was found that these species may form from hydrogen sulfide produced in enzymatic reactions or by utilizing the sulfur present in protein persulfides. Possible pathways of thiolated arsenical formation were proposed and supporting data for their existence provided. In addition to known mechanism of arsenic toxicity such as protein-binding and reactive oxygen formation, it was proposed that the utilization of thiols from protein persulfides during the formation of thiolated arsenicals may be an additional mechanism of toxicity. The toxicities of DMAV(GS), DMMTA V, and DMMTAV(GS) were evaluated in cancer cells, and the ability of these cells to take the compounds up were compared. When assessing the toxicity by exposing multiple myeloma cells to arsenicals externally, DMMTAV(GS) was much less toxic than DMAIII(GS) and DMMTAV, probably as a result of its very limited uptake (less than 10% and 16% of DMAIII(GS) and DMMTAV respectively).^

Integração e interdisciplinaridade no processo ensino/aprendizagem de projeto: o curso de Arquitetura e Urbanismo da Universidade Potiguar de Mossoró-RN

Training in Architecture and Urbanism with its general characteristic involves, in its nature, knowledge of various areas (technology, theory, history, representation, and design), being the space of design conception that place where the synthesis of this knowledge is reflected more clearly. We believe that the integrated work in the architectural curriculum can provide an overview of the project, thus contributing to better training of the architect. This research aims to reflect on the role of integration and interdisciplinary in teaching architectural design. This theme has been work recurrently by critics in the teaching area of project and events of the area as the seminars of the Projetar, highlighted by several authors to search integration as an essential pedagogical approach to design education. The work aims to contribute to reflection and awareness of those involved on the importance of integration in the architectural course of project processes. For this, we analyzed the potential and limits of this process in Architecture and Urbanism Course (CAU) at the Universidade Potiguar (UNP) Mossoró, which has the integration and interdisciplinary recorded since the Pedagogical Project of the Course. This analysis will be performed by observing the development of “interdisciplinary work” in the fifth term during the first half of 2014.1. This research concerns an exploratory qualitative study that aims to investigate specific issues on the teaching/learning architecture project and the integration in architecture courses, following a non-participant observation in architectural design classes in the fifth term of CAU/UnP/ Mossoró, and analysis of final products, which would be the work of the last unit of the semester, called “Interdisciplinary work”. Questionnaires for the teachers who participated in the process has been apply via email and analyzed. Reflection supports several other already carried out to identify the difficulties inherent in applying these principles satisfactorily. Noting, however, that interdisciplinarity, in fact, it goes beyond integration and is even more difficult to achieve. In addition to an educational project that incorporates these principles, such as the course of Architecture and Urbanism of the UNP-Mossoró, full adhesion it is necessary by the faculty and students of this teaching philosophy.

Integração e interdisciplinaridade no processo ensino/aprendizagem de projeto: o curso de Arquitetura e Urbanismo da Universidade Potiguar de Mossoró-RN

Training in Architecture and Urbanism with its general characteristic involves, in its nature, knowledge of various areas (technology, theory, history, representation, and design), being the space of design conception that place where the synthesis of this knowledge is reflected more clearly. We believe that the integrated work in the architectural curriculum can provide an overview of the project, thus contributing to better training of the architect. This research aims to reflect on the role of integration and interdisciplinary in teaching architectural design. This theme has been work recurrently by critics in the teaching area of project and events of the area as the seminars of the Projetar, highlighted by several authors to search integration as an essential pedagogical approach to design education. The work aims to contribute to reflection and awareness of those involved on the importance of integration in the architectural course of project processes. For this, we analyzed the potential and limits of this process in Architecture and Urbanism Course (CAU) at the Universidade Potiguar (UNP) Mossoró, which has the integration and interdisciplinary recorded since the Pedagogical Project of the Course. This analysis will be performed by observing the development of “interdisciplinary work” in the fifth term during the first half of 2014.1. This research concerns an exploratory qualitative study that aims to investigate specific issues on the teaching/learning architecture project and the integration in architecture courses, following a non-participant observation in architectural design classes in the fifth term of CAU/UnP/ Mossoró, and analysis of final products, which would be the work of the last unit of the semester, called “Interdisciplinary work”. Questionnaires for the teachers who participated in the process has been apply via email and analyzed. Reflection supports several other already carried out to identify the difficulties inherent in applying these principles satisfactorily. Noting, however, that interdisciplinarity, in fact, it goes beyond integration and is even more difficult to achieve. In addition to an educational project that incorporates these principles, such as the course of Architecture and Urbanism of the UNP-Mossoró, full adhesion it is necessary by the faculty and students of this teaching philosophy.

Efeitos da terapia laser de baixa intensidade associada ao exercício aeróbio no reparo de tenotomia do tendão de aquiles de ratos diabéticos

Diabetes Mellitus (DM ) is a complex disease that requires continuous medical care for the reduction of risk factors in addition to glycemic control. The typical hyperglycemia of this disease produces glycosylation of proteins and so the consequence is the accumulation of glycosylation final products in various human tissues, among them, the tendon. The aerobic exercise (AE) and the low level laser therapy (LLLT) have been used to treat tendinopathies in individuals with or without DM. Objective: The aim of this study was to watch the effect of the LLLT and the AE, in association, in partial tenotomy of the tissue repair of the Achilles tendon (AT) of diabetic rats. Methods: 91 animals were utilized and divided in to the following groups: control group (GC), injured control group (GCL), diabetic group (GD), diabetic group LLLT (GD – TLBI), diabetic group trained (GD - EX) and diabetic group trained laser (GD-EX+TLBI). The animals were submitted to intervention with AE, using a protocol with a progressive increase of time (12 to 60 min) and speed of (4 to 9 m/min), and the LLLT (660 nm laser, 10mW, 4 J/cm², single point for 16 seconds, three times for week). It was analyzed morphological, biomechanical and molecular characteristics. For data showing normal distribution was used one-way ANOVA test and post hoc Tukey and data without normal distribution was used Mann Whitney test and post hoc Dunn's. It was accepted p <0.05 for statistical significance Results: The biomechanical tests indicated major improvement in the GC and GD-EX+TLBI groups when compared with the diabetic groups in the following variables: maximum load, strain, absorbed energy, stress, cross section area, elastic modulus and energy density (p<0.05). The analysis through molecular biology indicated that the association of aerobic exercise and LLLT generated an increase of the collagen I gene expression and modulated the expression of the MMP2 and MMP9 (p<0.05). No observed any major improvement in the morphological variable studied. Conclusion: the LLLT associated with aerobic exercise promotes and increase of the mechanical properties, in the control of collagen I gene expression and of the MMP2 and MMP9 of the diabetic rats.

Fast and sensitive aflatoxin B1 and total aflatoxins ELISAs for analysis of peanuts, maize and feed ingredients

Aflatoxins are a group of carcinogenic compounds produced by Aspergillus fungi that can grow on different agricultural crops. Both acute and chronic exposure to these mycotoxins can cause serious illness. Due to the high occurrence of aflatoxins in crops worldwide fast and cost-effective analytical methods are required for the identification of contaminated agricultural commodities before they are processed into final products and placed on the market. In order to provide new tools for aflatoxin screening two prototype fast ELISA methods: one for the detection of aflatoxin B₁ and the other for total aflatoxins were developed. Seven monoclonal antibodies with unique high sensitivity and at the same time good cross-reactivity profiles were produced. The monoclonal antibodies were characterized and two antibodies showing IC₅₀ of 0.037 ng/mL and 0.031 ng/mL for aflatoxin B₁ were applied in simple and fast direct competitive ELISA tests. The methods were validated for peanut matrix as this crop is one of the most affected by aflatoxin contamination. The detection capabilities of aflatoxin B₁ and total aflatoxins ELISAs were 0.4 μg/kg and 0.3 μg/kg for aflatoxin B₁, respectively, which are one of the lowest reported values. Total aflatoxins ELISA was also validated for the detection of aflatoxins B₂, G₁ and G₂. The application of the developed tests was demonstrated by screening 32 peanut samples collected from the UK retailers. Total aflatoxins ELISA was further applied to analyse naturally contaminated maize porridge and distiller's dried grain with solubles samples and the results were correlated with these obtained by UHPLC-MS/MS method.

Composites and foams based on polylactic acid (PLA)

Cette étude est destinée à la production et à la caractérisation des composites d’acide polylactique (PLA) et des fibres naturelles (lin, poudre de bois). Le moussage du PLA et ses composites ont également été étudiés afin d’évaluer les effets des conditions de moulage par injection et du renfort sur les propriétés finales de ces matériaux. Dans la première partie, les composites constitués de PLA et des fibres de lin ont été produits par extrusion suivit par un moulage en injection. L’effet de la variation du taux de charge (15, 25 et 40% en poids) sur les caractéristiques morphologique, mécanique, thermique et rhéologique des composites a été évalué. Dans la deuxième étape, la poudre de bois (WF) a été choisie pour renforcer le PLA. La préparation des composites de PLA et WF a été effectuée comme dans la première partie et une série complète de caractérisations morphologique, mécanique, thermique et l’analyse mécanique dynamique ont été effectués afin d’obtenir une évaluation complète de l’effet du taux de charge (15, 25 et 40% en poids) sur les propriétés du PLA. Finalement, la troisième partie de cette étude porte sur les composites de PLA et de renfort naturel afin de produire des composites moussés. Ces mousses ont été réalisées à l’aide d’un agent moussant exothermique (azodicarbonamide) via le moulage par injection, suite à un mélange du PLA et de fibres naturelles. Dans ce cas, la charge d’injection (quantité de matière injectée dans le moule: 31, 33, 36, 38 et 43% de la capacité de la presse à injection) et la concentration en poudre de bois (15, 25 et 40% en poids) ont été variées. La caractérisation des propriétés mécanique et thermique a été effectuée et les résultats ont démontré que les renforts naturels étudiés (lin et poudre de bois) permettaient d’améliorer les propriétés mécaniques des composites, notamment le module de flexion et la résistance au choc du polymère (PLA). En outre, la formation de la mousse était également efficace pour le PLA vierge et ses composites car les masses volumiques ont été significativement réduites.

Cooperativa habitacional autofinanciável :uma alternativa de mercado à escassez de financiamento

As an example of what happened in Brazil in the 90s, it s noticed in Natal a new system of cooperative housing production which is done by advancing the users resources selffinancing. This system comes as an alternative for the real state market performance since the end of the National Housing Bank (BNH), in 1986. Self-financed housing cooperatives play an important social role by contributing to own housing acquisition by low-income population, without, however, becoming a mechanism of social interest housing production. It is important to consider that Brazil registers a housing deficit of 6.6 million housing units (IBGE 2000/Census), which, compared to 1991, shows an increment of 21.7% to a growth rate of 2.2% a year. This deficit figure has been deepening, mainly with the end of the National Housing Bank (BNH). The self-financed cooperative housing production broadens around the Metropolitan Region of Natal (RMN) and remains as an alternative to the lack of financing in the housing / real state market. In general, the aim of this work is to analyze the role of self-financing housing cooperatives on the housing production in the RMN, in order to identify their role in the real state market, in the own housing promotion and in the housing policy. The Universe of this study is performance of four housing cooperatives - CHAF-RN, COOPHAB-RN, MULTHCOOP e CNH - that work through self-financing. It is considered here an amount of 38 undertakings launched between 1993 and 2002, including 8143 housing units. The methodology adopted consists of bibliographic, documental and field research. As a result, actions like brokerage, marketing, speculation, and the criteria to define places for undertakings and final products, show how close they are to the housing market production. As a matter of fact, this short distance explains why the self-financed cooperative production for social interest housing is still limited. This reinforces the theory that it is necessary to define and implement a subsidized housing policy to serve the low-income Brazilian population