Contribuição da fitoquímica para o desenvolvimento de um país emergente

The sustainable development of an emergent country is dependent on a consistent scientific, technologic and innovative policy, on nature and biodiversity, on a rational exploration of natural resources to feeding, social advance and economical aim along with maintenance of health and diseases treatment. Phytochemical investigations may be used to contribute with development throughout undergraduate and graduate career preparing professionals with qualification to these activities, as researcher and professor, including discovering and divulgation of new scientific knowlegments. The role of organic compounds produced by secondary metabolism of plants in the development of new drugs is presented (e. g.) throughout exposition using examples of features involved in this activity, since the recognition of a plant-derived popular medicine, until the laboratory semi-synthesis of its main constituents. Several aspects related to the use of some vegetable species in treatment of many tropical diseases are pointed. Economical and social importance of isolation, structural characterization, pharmacological investigation and chemical transformations of new natural organic substances isolated from the plants are related.

Em busca da conservação ambiental: a contribuição da percepção ambiental para a formação e atuação dos profissionais da Química

Planet transformations caused by human intervention in the last 200 years are largely due to chemical impact. Therefore, this study aimed to identify and analyze the environmental perception of undergraduate students and lecturers in the Chemistry course of the Federal University of Lavras, accounting for the topics "Environmental Definition" and "Relationship between Chemistry and Environment". Two thematic axes for discussion were proposed using theories of Social Representation and Environmental Complexity, with the aim of stimulating the conservationist reasoning and actions. Such axes were proposed to give support to the education of chemists at the undergraduate level.

Glicerol: um breve histórico e aplicação em sínteses estereosseletivas

Presently glycerol is considered a co-product of biodiesel industry. As the biodiesel production is exponentially increasing, glycerol generated from the transesterification of vegetable oils and fats is also being produced on a large scale, and turned out to be essential seeking for novel alternatives to the consumption of the extra volume, in crude and/or as derivatives high added value. This review mainly deals with chemical and enzymatic transformations of glycerol to obtain chiral building blocks for synthesis of pharmaceuticals and natural products.

Pyrrolizidine alkaloids of senecio sp from Peru

Six pyrrolizidine alkaloids (PAs) (two saturated macrocyclic, three unsaturated macrocyclic and one unsaturated seco-macrocyclic) were isolated from native Peruvian Senecio species. The structures of these alkaloids were established by a complete NMR spectroscopic analysis, chemical transformations and comparison of their NMR data with those published for similar alkaloids. Three PAs were then tested for antifungal activity against Fusarium moniliforme, F. (Sheldon), F. oxysporum fs. lycopersici (Scheldt) and F. solani (Mart), no significant activity being observed.

Synthesis of geranylhydroquinone derivatives with potencial cytotoxic activity

Natural geranylhydroquinone 1 and geranyl-p-methoxyphenol 2 were prepared by Electrophilic Aromatic Substitution (EAS) reactions between geraniol and 1,4-hydroquinone or p-methoxyphenol respectively, using BF3∙Et2O as a catalyst. Furthermore, natural geranylquinone 3, geranyl-1,4-dimethoxyquinone 4 and the new geranyl-4-methoxyphenyl acetate 5 were obtained by chemical transformations of 1 and 2. The compounds were evaluated for their in vitro cytotoxicity activities against cultured human cancer cells of PC-3 human prostate cancer, MCF-7 and MDA-MB-231 breast carcinoma, and Dermal Human Fibroblasts DHF. IC50 values were in the µM range.

Aspectos estruturais de algumas neolignanas hidrobenzofurânicas

The neolignans are defined as dimers of allylphenol and propenylphenol between itself or crossed, whose bond does not occur by the 8-8' carbons like lignans. This review centered on stereochemical aspects of the hydrobenzofuran type, a widespread skeleton among neolignans. The chemical structures established based on spectrometric data are registered in the literature. The absolute configurations reported previously were determined by chiroptical techniques. Some chemical transformations with neolignans, performed in previous studies, afforded products which are accumulated in other vegetal species and contributed to assign the unknown stereochemistry of these natural compounds. Possible biosynthetic pathways are also proposed.

Un método para enseñar el porqué suceden las reacciones químicas

A methodology is proposed for explaining one of the central questions in the teaching of general chemistry courses to freshman students: why do chemical transformations occur? The answer to this question is based on thermodynamics but we propose arriving at an answer in a more intuitive way by using computational tools in a bid to increase the motivation of students for learning chemistry.

Caracterização físico-química do óleo essencial da Siparuna guianensis Aublet

Thermal and spectroscopic analyses of essential oil extracted from Siparuna guianensis Aublet, an aromatic plant belonging to medicinal ethnobotany family Siparunaceae, were carried out. The plant is known throughout the North and Northeast of Brazil by the name negramina and has wide application as a natural insect repellent. Thermogravimetric analyses were correlated with the Arrhenius Equation to provide kinetic parameters of evaporation, including activation energy and frequency factor. Differential scanning calorimetric analysis showed the presence of an exothermic oxidation peak, probably as a result of transformations and decomposition of the solid structure before melting.

TRIHALOMETANOS EM ÁGUA POTÁVEL E RISCOS DE CÂNCER: SIMULAÇÃO USANDO POTENCIAL DE INTERAÇÃO E TRANSFORMAÇÕES DE BÄCKLUND

We briefly investigated the well-known correlation of trihalomethanes, present in fresh water, with cancer hazard in humans. A transient alternative method of chemical simulation using Bäcklund Transformations and Quantum Mechanics is presented. Finally, the method was applied to simulate the interaction between Trichloridemethane and Alanine - as well as its amino and carboxyl groups.

Kadonnutta me-politiikkaa etsimässä

Kirjallisuusarvostelu

Ptolemaioksen lauseen yleistyksestä tasokäyrien tasaisuuden luonnehtimiseksi

Tutkielma tarkastelee tasokäyrien tasaisuuden mittaamista lukuarvona, jonka määritelmä perustetaan geometriseen Ptolemaioksen lauseeseen. Tarkoituksena on selvittää, missä määrin luotu mitta sopii käyrien tasaisuuden luonnehdinnaksi, mutta päämääränä on myös määrittää tavanomaisimpien tasokuvioiden tasaisuus mitalla mitattuina. Mitattava arvo on tullut jo aikaisemmissa tutkimuksissa esille, ja sen perusteella voidaan muotoilla välttämätön ja riittävä ehto niin sanotuille kvasiympyröille. Myös yhteys K-kvasiympyröitä kuvaavaan suureeseen K on olemassa. Silti arvon tutkimus on toistaiseksi ollut vähäistä, joten tutkielma syventyy arvon määrittämisen lisäksi uusien menetelmien kehittämiseen. Pääasiallisena työkaluna tässä tehtävässä ovat Möbius-kuvaukset. Lukuarvon tutkimuksen ohella selvitetään sen yhteyksiä toiseen käyräkohtaiseen vakioon. Tasoalueille määritelty uniformisuusvakio ilmentää eräässä esitysmuodossa samankaltaisia piirteitä kuin alueen reunakäyrälle kehitetty tasaisuuden mitta. Tähän näennäiseen yhteyteen perustuva tutkimushypoteesi osoitetaan alkuperäisessä muodossaan osittain vääräksi, mutta otaksuma tulee jalostetuksi saatujen tulosten perusteella. Vaikka tyhjentävää kuvausta yhteydestä ei saada, tutkimus paljastaa samankaltaisuuksia ja eroja tarkasteltavien lukujen luonteissa.

Preparing for CRIS: Challenges and Opportunities for Systems Integration at Finnish Universities

Poster at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014

Rigorous development of safety-critical systems

Nowadays, computer-based systems tend to become more complex and control increasingly critical functions affecting different areas of human activities. Failures of such systems might result in loss of human lives as well as significant damage to the environment. Therefore, their safety needs to be ensured. However, the development of safety-critical systems is not a trivial exercise. Hence, to preclude design faults and guarantee the desired behaviour, different industrial standards prescribe the use of rigorous techniques for development and verification of such systems. The more critical the system is, the more rigorous approach should be undertaken. To ensure safety of a critical computer-based system, satisfaction of the safety requirements imposed on this system should be demonstrated. This task involves a number of activities. In particular, a set of the safety requirements is usually derived by conducting various safety analysis techniques. Strong assurance that the system satisfies the safety requirements can be provided by formal methods, i.e., mathematically-based techniques. At the same time, the evidence that the system under consideration meets the imposed safety requirements might be demonstrated by constructing safety cases. However, the overall safety assurance process of critical computerbased systems remains insufficiently defined due to the following reasons. Firstly, there are semantic differences between safety requirements and formal models. Informally represented safety requirements should be translated into the underlying formal language to enable further veri cation. Secondly, the development of formal models of complex systems can be labour-intensive and time consuming. Thirdly, there are only a few well-defined methods for integration of formal verification results into safety cases. This thesis proposes an integrated approach to the rigorous development and verification of safety-critical systems that (1) facilitates elicitation of safety requirements and their incorporation into formal models, (2) simplifies formal modelling and verification by proposing specification and refinement patterns, and (3) assists in the construction of safety cases from the artefacts generated by formal reasoning. Our chosen formal framework is Event-B. It allows us to tackle the complexity of safety-critical systems as well as to structure safety requirements by applying abstraction and stepwise refinement. The Rodin platform, a tool supporting Event-B, assists in automatic model transformations and proof-based verification of the desired system properties. The proposed approach has been validated by several case studies from different application domains.

Silicon-containing species in used lube oil re-refining

Nowadays, the re-refining of the used lube oils has gained worldwide a lot of attention due to the necessity for added environmental protection and increasingly stringent environmental legislation. One of the parameters determining the quality of the produced base oils is the composition of feedstock. Estimation of the chemical composition of the used oil collected from several European locations showed that the hydrocarbon structure of the motor oil is changed insignificantly during its operation and the major part of the changes is accounted for with depleted oil additives. In the lube oil re-refining industry silicon, coming mainly from antifoaming agents, is recognized to be a contaminant generating undesired solid deposits in various locations in the re-refining units. In this thesis, a particular attention was paid to the mechanism of solid product formation during the alkali treatment process of silicon-containing used lube oils. The transformations of a model siloxane, tetramethyldisiloxane (TMDS), were studied in a batch reactor at industrially relevant alkali treatment conditions (low temperature, short reaction time) using different alkali agents. The reaction mechanism involving solid alkali metal silanolates was proposed. The experimental data obtained demonstrated that the solids were dominant products at low temperature and short reaction time. The liquid products in the low temperature reactions were represented mainly by linear siloxanes. The prolongation of reaction time resulted in reduction of solids, whereas both temperature and time increase led to dominance of cyclic products in the reaction mixture. Experiments with the varied reaction time demonstrated that the concentration of cyclic trimer being the dominant in the beginning of the reaction diminished with time, whereas the cyclic tetramer tended to increase. Experiments with lower sodium hydroxide concentration showed the same effect. In addition, a decrease of alkali agent concentration in the initial reaction mixture accelerated TMDS transformation reactions resulting in solely liquid cyclic siloxanes yields. Comparison of sodium and potassium hydroxides applied as an alkali agent demonstrated that potassium hydroxide was more efficient, since the activation energy in KOH presence was almost 2-fold lower than that for sodium hydroxide containing reaction mixture. Application of potassium hydroxide for TMDS transformation at 100° C with 3 hours reaction time resulted in 20 % decrease of solid yields compared to NaOH-containing mixture. Moreover, TMDS transformations in the presence of sodium silanolate applied as an alkali agent led to formation of only liquid products without formation of the undesired solids. On the basis of experimental data and the proposed reaction mechanism, a kinetic model was developed, which provided a satisfactory description of the experimental results. Suitability of the selected siloxane as a relevant model of industrial silicon-containing compounds was verified by investigation of the commercially available antifoam agent in base-catalyzed conditions.

Transformation of carbon dioxide to diethyl carbonate over ceria and ceria-supported catalysts

Carbon dioxide is regarded, nowadays, as a primary anthropogenic greenhouse gas leading to global warming. Hence, chemical fixation of CO2 has attracted much attention as a possible way to manufacture useful chemicals. One of the most interesting approaches of CO2 transformations is the synthesis of organic carbonates. Since conventional production technologies of these compounds involve poisonous phosgene and carbon monoxide, there is a need to develop novel synthetic methods that would better match the principles of "Green Chemistry" towards protection of the environment and human health. Over the years, synthesis of dimethyl carbonate was under intensive investigation in the academia and industry. Therefore, this study was entirely directed towards equally important homologue of carbonic esters family namely diethyl carbonate (DEC). Novel synthesis method of DEC starting from ethanol and CO2 over heterogeneous catalysts based on ceria (CeO2) was studied in the batch reactor. However, the plausible drawback of the reaction is thermodynamic limitations. The calculated values revealed that the reaction is exothermic (ΔrHØ298K = ─ 16.6 J/ ) and does not occur spontaneously at rooms temperature (ΔrGØ 298K = 35.85 kJ/mol). Moreover, co-produced water easily shifts the reaction equilibrium towards reactants excluding achievement of high yields of the carbonate. Therefore, in-situ dehydration has been applied using butylene oxide as a chemical water trap. A 9-fold enhancement in the amount of DEC was observed upon introduction of butylene oxide to the reaction media in comparison to the synthetic method without any water removal. This result confirms that reaction equilibrium was shifted in favour of the desired product and thermodynamic boundaries of the reaction were suppressed by using butylene oxide as a water scavenger. In order to obtain insight into the reaction network, the kinetic experiments were performed over commercial cerium oxide. On the basis of the selectivity/conversion profile it could be concluded that the one-pot synthesis of diethyl carbonate from ethanol, CO2 and butylene oxide occurs via a consecutive route involving cyclic carbonate as an intermediate. Since commercial cerium oxide suffers from the deactivation problems already after first reaction cycle, in-house CeO2 was prepared applying room temperature precipitation technique. Variation of the synthesis parameters such as synthesis time, calcination temperature and pH of the reaction solution turned to have considerable influence on the physico-chemical and catalytic properties of CeO2. The increase of the synthesis time resulted in high specific surface area of cerium oxide and catalyst prepared within 50 h exhibited the highest amount of basic sites on its surface. Furthermore, synthesis under pH 11 yielded cerium oxide with the highest specific surface area, 139 m2/g, among all prepared catalysts. Moreover, CeO2─pH11 catalyst demonstrated the best catalytic activity and 2 mmol of DEC was produced at 180 oC and 9 MPa of the final reaction pressure. In addition, ceria-supported onto high specific surface area silicas MCM-41, SBA-15 and silica gel were synthesized and tested for the first time as catalysts in the synthesis of DEC. Deposition of cerium oxide on MCM-41 and SiO2 supports resulted in a substantial increase of the alkalinity of the carrier materials. Hexagonal SBA-15 modified with 20 wt % of ceria exhibited the second highest basicity in the series of supported catalysts. Evaluation of the catalytic activity of ceria-supported catalysts showed that reaction carried out over 20 wt % CeO2-SBA-15 generated the highest amount of DEC.