Alilação e crotilação catalítica e enantiosseletiva de aldeídos

The field of chiral catalysis has experienced explosive growth over the last two decades. By now, many of the classical reactions in organic synthesis can be carried out efficiently in asymmetric manner. As one of the fundamental and powerful C-C bond-forming reactions, enantioselective catalytic allylation (ECA) and crotylation (ECC) of aldehydes has attracted considerable attention. In this article, we present an overview about the importance of chiral Lewis acids and bases in catalytic enantioselective addition of allyl- and crotyl metals to aldehydes and the application of this methodology in the total synthesis of natural and non-natural products.

Recentes avanços e novas perspectivas dos eletrodos íon-seletivos

This paper describes the recent progress in the development of polymeric membranes for ion-selective electrodes. The importance of knowing the mechanism of potential development in membranes for ion-selective electrodes to reach lower detection limits and improve selectivity are discussed. Recent advances and future trends of research on ion-selective electrodes are also reported.

Um novo método para quantificar mercúrio orgânico (Hg orgânico) empregando a espectrometria de fluorescência atômica do vapor frio

In this work a simple and sensitive procedure to extract organic mercury from water and sediment samples, using methylene chloride in acidic media followed by CVAFS quantification has been developed. The method was evaluated for possible interferents, using different inorganic mercury species and humic acid, no effects being observed. The detection limit for organic mercury was 160 pg and 396 pg for water and sediment samples respectively. The accuracy of the method was evaluated using a certified reference material of methylmercury (BCR-580, estuarine sediment). Recovery tests using methylmercury as surrogate spiked with 1.0 up to 30.0 ng L-1 ranged from 90 up to 109% for water samples, whereas for sediments, recoveries ranged from 57 up to 97%.

Utilização de um monitor de vídeo como fonte de alta tensão para eletroforese capilar

This article describes the use of a conventional CRT monitor as a high voltage power supply for capillary electrophoresis. With this monitor, a 23-kV high voltage with a ripple of 1.32% was observed. The reproducibility of the applied high voltage was evaluated by measuring the standard deviations of peak area and migration time for five consecutive injections of a test mixture containing potassium, sodium, and lithium cations at 50 mmol L-1. The errors were about 2.5% and 0.6% for peak area and migration time, respectively. The maximum current tested was about 180 mA, which covers most capillary electrophoresis applications. This system has been successfully used for several months, maintaining the desired level of performance.

Estudo teórico da interação existente entre a artemisinina e o heme

The purpose of this work is to study theoretically stereoelectronic aspects of the interaction between heme and artemisinin in the transitional heme-artemisinin complex. Through semi-empirical calculations using the PM3 method, the potential energy barrier of artemisinin rotation relative to heme in the heme-artemisinin complex was studied in vacuum and in the partially solvated state. The minimum heat of formation obtained for the complex with and without water molecules is -702.39 and -100.86 kcal mol-1, respectively, which corresponds to the dihedral angle C-Fe-O1-O2 of 43.93º and 51.90º around the iron-oxygen O1 bond, respectively. The water molecules bind to heme via 13 hydrogen bonds and O-H O and 6 C-H O interactions, which accounts for -67.23 kcal mol-1. It is observed that the inclusion of water molecules does not affect significantly the stability of the heme-artemisinin complex.

Descrições estruturais cristalinas de zeólitos

Crystalline structures of zeolites can be studied using different representations: the internal symmetry obtained by X-Ray or neutron diffraction crystallography techniques or a systematic analysis of the basic structural units which can be arranged to build the geometries of each kind of zeolite. In this work the basic concepts of three building units, SBU (Secondary Building Units), SSU (Structural SubUnits) and PBU (Periodic Building Units) are presented. The properties of the resulting crystalline structures are discussed (pores, cavities, channels), describing the influence of each one of these properties in processes of physical-chemical interest. Representative case studies of known zeolite crystalline structures are also discussed in terms of their space group classification.

Pectinases: aplicações industriais e perspectivas

Pectic substances are structural heteropolysaccharides that occur in the middle lamellae and primary cell walls of higher plants. They are composed of partially methyl-esterified galacturonic acid residues linked by alpha-1, 4-glycosidic bonds. Pectinolytic enzymes are complex enzymes that degrade pectic polymers and there are several classes of enzymes, which include pectin esterases, pectin and pectate lyases and polygalacturonases. Plants, filamentous fungi, bacteria and yeasts are able to produce pectinases. In the industrial world, pectinases are used in fruit juice clarification, in the production of wine, in the extraction of olive oil, fiber degumming and fermentation of tea, coffee and cocoa.

Conseqüências da análise incorreta de experimentos blocados

Errors are always present in experimental measurements so, it is important to identify them and understand how they affect the results of experiments. Statistics suggest that the execution of experiments should follow random order, but unfortunately the complete randomization of experiments is not always viable for practical reasons. One possible simplification is blocked experiments within which the levels of certain factors are maintained fixed while the levels of others are randomized. However this has a cost. Although the experimental part is simplified, the statistical analysis becomes more complex.

Ecomateriais: desenvolvimento e aplicação de materiais porosos funcionais para proteção ambiental

Fundamental aspects of the conception and applications of ecomaterials, in particular porous materials in the perspective of green chemistry are discussed in this paper. General recommendations for description and classification of porous materials are reviewed briefly. By way of illustration, some case studies of materials design and applications in pollution detection and remediation are described. It is shown here how different materials developed by our groups, such as porous glasses, ecomaterials from biomass and anionic clays were programmed to perform specific functions. A discussion of the present and future of ecomaterials in green chemistry is presented along with important key goals.

Experimentação em química de compostos organometálicos: preparação do cloreto de dicarbonilciclopentadienilferro(II)

In this work, we describe a new method for obtaining [Fe(CO)2[(eta5-C5H5)Cl] employing simple techniques and low-cost reagents. It is worth mentioning that this method is faster than others reported in the literature. It was applied in laboratory classes for undergraduate students, exploring different concepts in organometallic chemistry and discussing the steps involved in the synthetic route.

Determinação do perfil de compostos voláteis e avaliação do sabor e aroma de bebidas produzidas a partir da erva-mate (Ilex paraguariensis)

Volatile compounds from green and roasted yerba mate were analyzed by gas chromatography/mass spectrometry and the flavor profile from yerba mate beverages was determined by descriptive quantitative analyses. The main compounds tentatively identified in green mate were linalool, alpha-terpineol and trans-linalool oxide and in roasted mate were (E,Z)-2,4-heptadienal isomers and 5-methylfurfural. Green mate infusion was qualified as having bitter taste and aroma as well as green grass aroma while roasted mate was defined as having a smooth, slightly burnt aroma. The relationship between the tentatively identified compounds and flavor must be determined by olfatometric analysis.

Interferentes endócrinos no ambiente

Although the hypothesis that environmental chemicals may exhibit endocrine disrupting effects is not new, the issue has been a growing level of concern due to reports of increased incidences of endocrine-related disease in humans, including declining male fertility, and more significantly, to adverse physiological effects observed in wildlife where cause and effect relationships are more evident. The list of endocrine disrupting chemicals (EDCs) includes a range of anthropogenic compounds, phytoestrogens, naturally occurring sex steroids and synthetic estrogens. Within the aquatic environment, the presence of EDCs has concerned many scientists and water quality regulators. Discharge of effluents from treatment facilities is likely to be a significant source of input of contaminants to many systems, and the potential for concentration of hydrophilic compounds and transformation products within sludges has implications for their disposal. Then, understanding the processes and the fate of EDCs on the environment, as well as the mechanisms of endocrine disruption, may facilitate controlling or limiting exposure of both humans and the environment to these compounds.

Caracterização do complexo de inclusão ropivacaína: beta-ciclodextrina

Characteriza of the inclusion complex ropivacaine: beta-cyclodextrin. Ropivacaine (RVC) is a widely used local anesthetic. The complexation of RVC with beta-cyclodextrin (beta-CD) is of great interest for the development of more efficient local anesthetic formulations. The present work focuses on the characterization of the RVC:beta-CD complex by nuclear magnetic resonance (NMR). The stoichiometry of the complex is 1:2 RVC:beta-CD. DOSY-NMR shows that the association constant is 55.5 M-1. Longitudinal relaxation time results show that RVC changes its mobility in the presence of beta-CD. This study is focused on the physicochemical characterization of inclusion complexes that are potentials options for pain treatment.

A importância das revistas Química Nova e Journal of the Brazilian Chemical Society no crescimento da área de química no Brasil

Quimica Nova and the Journal of the Brazilian Chemical Society are two examples of successful initiatives taken by the Brazilian Chemical Society (SBQ - Sociedade Brasileira de Química), and may serve as models for the scientific societies of developing countries. Pillars of the SBQ, these two periodicals are undeniable demonstrations that idealism, utopia and dignity are the essential ingredients for transforming dreams into reality. Few believed that the Brazilian chemical community would one day have, as it does today, two scientific research periodicals indexed in the principal international data banks.

Estudo da capacidade de complexação e sua relação com algumas variáveis ambientais em cinco represas do Rio Tietê/Brasil

The copper and cadmium complexation properties in natural sediment suspensions of reservoirs of the Tietê River were studied using the solid membrane copper and cadmium ion-selective electrodes. The complexation and the average conditional stability constants were determined under equilibrium conditions at pH=6.00 ± 0.05 in a medium of 1.0 mol L-1 sodium nitrate, using the Scatchard method. The copper and cadmium electrodes presented Nernstian behavior from 1x10-6 to 1x10-3 mol L-1 of total metal concentration. Scatchard graphs suggest two classes of binding sites for both metals. A multivariate study was done to correlate the reservoirs and the variables: complexation properties, size, total organic carbon, volatile acid sulfide, E II and pH.