Table of contents
Química Nova, Volume: 29, Issue: 1, Published: 2006Química Nova, Volume: 29, Issue: 1, Published: 2006
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Editorial Desafios e oportunidades |
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Artigo Photochemistry of alpha,alpha-dimethylvalerophenone adsorbed on microcrystalline cellulose Behrens, Maria das Dores D. Netto-Ferreira, José Carlos Abstract in English: Irradiation of a,a-dimethylvalerophenone (1) adsorbed on microcrystalline cellulose employing methanol as the solvent shows a Norrish Type II/Type I ratio of 1.0±0.1. In solution, values of 2.3±0.3 in benzene and 8.7±2.0 in terc-butanol were obtained. The cyclization/elimination ratio for the Norrish Type II reaction of 1 shows values of 1.2±0.3 in cellulose, 17.9±2.7 in benzene and 3.2±03 in terc-butanol. When samples of 1/microcrystalline cellulose were prepared employing n-hexane, the Type II/Type I (29.5±2.9) and the cycl/elim (113.3±12.1) ratios were dramatically modified. These results demonstrate the difference in the behavior of 1 when entrapped in the cellulose chains or adsorbed on the cellulose surface. |
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Artigo Color removal in reactive dye solutions by UV/H2O2 oxidation Araujo, Fabiana Valéria da Fonseca Yokoyama, Lídia Teixeira, Luiz Alberto César Abstract in English: This paper summarizes the result of a degradation test of two azo-reactive dyes (Reactive Blue 214, Reactive Red 243) under UV irradiation in the presence of H2O2. Five different doses of hydrogen peroxide (0 mM, 5 mM, 10 mM, 20 mM and 30 mM) at constant initial concentration of the substrate (100 mg/L) were used. The radiation source were three 15 W-lamps. Complete destruction of the color of the solutions was attained in 40-50 min of irradiation. UV/H2O2 proved capable of complete discoloration and degradation of the above azo reactive dyes. |
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Artigo Electrochemical study of a novel cyanide free galvanic plating solution of alkaline zinc Silva, Gecílio P. da Freire, Nacélio S. Matos, Diogo E. de Correia, Adriana N. Lima-Neto, Pedro de Abstract in English: A systematic electrochemical study of a novel cyanide free galvanic plating solution of alkaline zinc is presented. Cell Hull tests and potentiodynamic linear polarization measurements were carried out to evaluate the influence of operational parameters, such as concentration, current efficiency and degradation of additives. The stability of the bath was assessed by a long term test during 40 h at 200 A m-2. The morphology of the coatings was characterized by scanning electron microscopy. The results showed good performance of the plating solution. The cost is similar to that of the commercial cyanide bath and lower than that of the commercial cyanide free bath. |
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Artigo Treatment of landfill leachates by heterogeneous photocatalysis integrated to a conventional biological process Morais, Josmaria Lopes de Sirtori, Carla Peralta-Zamora, Patricio G. Abstract in English: The chemical and microbiological decomposition of the garbage deposited in landfills leads to the generation of a dark and malodorous liquid residue that shows a chemical composition of extreme variability and complexity. When matured, the leachates show low biodegradability, which makes it difficult to treat by conventional biological processes. In this work a new strategy for the treatment of landfill leachates is proposed, involving a preliminary treatment by heterogeneous photocatalysis followed by an activated sludge system. The results demonstrate that photochemical treatments of 60 and 90 min significantly enhance the leachates' biodegradability favoring subsequent biological treatment. The biodegradability rate (BOD/COD) was also greatly enhanced. |
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Artigo Comparison of the efficiency of ozonation and catalytic ozonation (Mn II and Cu II) in phenol degradation Assalin, Márcia Regina Silva, Priscila Lima da Durán, Nelson Abstract in English: This paper discusses the results obtained with homogeneous catalytic ozonation [Mn (II) and Cu (II)] in phenol degradation. The reduction of total phenols and total organic carbon (TOC) and the ozone consumption were evaluated. The efficiency in phenol degradation (total phenol removal) at pH 3, with the catalytic process (Mn (II)), increased from 37% to 55% while the TOC removal increased from 4 to 63% in a seven-minute treatment. The ozonation process efficiency at pH 10 was 43% and 39% for phenol and TOC removal, respectively. The presence of both metallic ions (Mn2+ and Cu+2) in the ozonation process resulted in a positive effect. |
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Artigo Study of effects of silicon and phosphorus in reducing the availability of heavy metals in mining area Paim, Lilian Aparecida Carvalho, Ruy Abreu, Celeste Maria Patto Guerreiro, Mário César Abstract in English: This study was developed with a soil contaminated by heavy metals, with the purpose of evaluating the action of silicon and phosphorus as protection agents through simple extractions by DTPA. The collected samples were prepared and incubated with five doses of silicon and five doses of phosphorus, with four replicates, amounting to 100 experimental units. After 30 and 60 days, samples of each treatment were collected, submitted to pH analyses and simple extraction by DTPA. The amounts of DTPA-extracted metals depended on the doses of silicon and phosphorus and on the pH. Treatments with silicon and phosphorus was efficient in decreasing the availability of heavy metals in soil. |
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Artigo Chitosan microspheres crosslinked with tripolyphosphate used for the removal of the acidity, iron (III) and manganese (II) in water contaminated in coal mining Laus, Rogério Laranjeira, Mauro C. M. Martins, Amarildo O. Fávere, Valfredo T. Pedrosa, Rozângela C. Benassi, Jean C. Geremias, Reginaldo Abstract in English: Considerable attention has been paid to chitosan and derivatives as efficient adsorbents of pollutants such as metal ions and dyes in aqueous medium. Nevertheless, no report can be found on the remedial actions of chitosan microspheres crosslinked with tripolyphosphate to control acidity, iron (III) and manganese (II) contents in wastewaters from coal mining. In this work, chitosan microspheres crosslinked with tripolyphosphate were used for the neutralization of acidity and removal of Fe (III) and Mn (II) from coal mining wastewaters. The study involved static and dinamic methods. The neutralization capacity of the surface of the static system was 395 mmol of H3O+ per kilogram of microspheres, higher than that of the dynamic one (223 mmol kg-1). The removal of Fe(III) in wastewater was of 100% and that of Mn(II) was 90%. |
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Artigo Evaluation of metal content in sediments of the Betari River in the Parque Estadual Turístico do Alto Ribeira: PETAR-, São Paulo, Brazil Cotta, Jussara Aparecida Oliveira Rezende, Maria Olímpia Oliveira Piovani, Mônica R. Abstract in English: The subsoil of the Vale do Ribeira was the focus of mining industries for the exploration of lead, mainly inside the park - PETAR. Despite the fact that the exploration has ended, the environmental effects of those activities are still present, due to great amounts of heavy metals that are leached. Concentrations of pseudo-total and bioavailable metals were determined in sediment samples of the Betari River, using atomic absorption spectrometry. The results demonstrated that the sediments are contaminated by Pb, Zn and Cu. The findings can contribute to an efficient and environmentally and economically adequate management of the park, for the conservation and the protection of the area. |
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Artigo Determination of nitrogen forms and total nitrogen in petroleum reservoir rocks by steam distillation and the indophenol method Silva, Lílian Irene Dias da Carneiro, Manuel Castro Emídio, Vanessa dos Santos Henrique Junior, Sérgio de Souza Monteiro, Maria Inês Couto Abstract in English: Several extraction procedures are described for the determination of exchangeable and fixed ammonium, nitrate + nitrite, total exchangeable nitrogen and total nitrogen in certified reference soils and petroleum reservoir rock samples by steam distillation and indophenol method. After improvement of the original distillation system, an increase in worker safety, a reduction in time consumption, a decrease of 73% in blank value and an analysis without ammonia loss, which could possibly occur, were achieved. The precision (RSD < 8%, n = 3) and the detection limit (9 mg kg-1 NH4+-N) are better than those of published procedures. |
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A novel metabolite from the Chilean mollusk Siphonaria lessoni
Rovirosa, Juana
San-Martín, Aurelio
Abstract in English: A new and two previously known metabolites possessing a polypropionate carbon skeleton have been isolated from the marine gastropod mollusk Siphonaria lessoni, collected at Chilean coasts. Their structures have been determined by spectroscopical methods. |
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Artigo Estimate of ammonia fluxes at the air-sea interface in the Guanabara Bay: a preliminary study Guimarães, Giselle Parno Mello, William Zamboni de Abstract in English: In the begining of April 2004, concentrations of NHx (NH3 + NH4+) were measured in surface waters of the Guanabara Bay. Concentrations varied from 2 to 143 mmol L-1. Ammonia exchange at the air-sea interface was quantified using a numerical model. No measurement of NH3 concentration in air (c air) was performed. Thus, calculations of NH3 flux were based on the assumptions of c air = 1 and 5 µg m-3. Fluxes were predominantly from the water to the atmosphere and varied from -20 to almost 3500 µg N m-2 h-1. |
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Artigo Environmental diagnostic of metals and organochlorinated compounds in streams near sugar cane plantations activity (São Paulo State, Brazil) Corbi, Juliano José Strixino, Susana Trivinho Santos, Ademir do Del Grande, Marcelo Abstract in English: Sugar cane cultivation in the State of São Paulo has expanded in the last years, with an annual production of 200•10(6) t in an area of 2.5• 10(6) hectares. The use of herbicides, pesticides and fertilizers in sugar cane plantations, together with deforestation of riparian vegetation, have caused impacts on the hydric resources of the adjacent areas. The aim of this work is to evaluate the influence of sugar cane plantations on streams in the central region of the State of São Paulo, studying 16 organochlorinated compounds and 7 metals (Cu, Fe, Cd, Zn, Mn, Cr and Ni) found in the sediments of 11 streams. The results show that there is a higher concentration of metals and organochlorinated compounds in streams without riparian vegetation when compared to forested areas. |
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Artigo Evaluation of inorganic and organic contaminants in alcohol fuel by capillary electrophoresis Pereira, Elisabete A. Tavares, Marina F. M. Stevanato, Alessandra Cardoso, Arnaldo A. Abstract in English: This work reports the analysis of inorganic and organic contaminants in alcohol fuel samples using capillary electrophoresis. Chloride and sulfate were analyzed in nitrate/ monochloroacetic acid at 10 mmol L-1 concentration each under indirect UV detection (210 nm). The analysis of aldehydes is based on the 216 nm detection of 3-methyl-2-benzothiazoline hydrazone adducts. The running buffer consisted of 20 mmol L-1 tetraborate , 40 mmol L-1 sodium dodecyl sufate and 12 mmol L-1 beta-ciclodextrin. Both methodologies were applied to real samples indicating inorganic ion concentrations from 0.15 to 6.64 mg kg-1 and aldehydes from 32.0 to 91.3 mg L-1. |
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Artigo Development of restricted-access media chromatographic columns protein-immobilized and their evaluation for the analysis of drugs by direct injection of human plasma Lima, Virgínia Veronica de Cassiano, Neila Maria Cass, Quezia Bezerra Abstract in English: A series of bovine serum albumin-immobilized supports have been prepared and used as restricted access media (RAM) columns. Restricted-access supports combine size-exclusion of proteins and other high-molar-mass matrix components with the simultaneous enrichment of low-molar mass analytes. These characteristics were chromatographically evaluated for the columns. The RAM-BSA (Bovine Serum Albumin) columns showed excellent performance for exclusion of human plasma protein with good retention capacity for a series of acidic, basic, and neutral drugs. |
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Artigo The use of centrifuged sludge from a water treatment plant (WTP) in portland cement concrete matrices for reducingthe environmental impact Hoppen, Cinthya Portella, Kleber F. Joukoski, Alex Trindade, Eduardo M. Andreóli, Cléverson V. Abstract in English: An alternative application of the humid sludge from the Passaúna WTP, located in Curitiba's metropolitan area, is proposed for concrete structures, partially replacing aggregates and cement. For the investigation, a reference concrete and four concrete mixtures with sludge were produced, and from these, two mixtures, containing 4% and 8% of sludge (m/m), were analyzed by different techniques: X ray fluorescence, X ray diffraction, thermo-gravimetric analysis, physicochemical analysis, compressive strength, etc. The properties were evaluated and the results indicate that the mixtures can be applied in different situations as cast structures for construction of concrete walls. Mixtures with more than 4% of sludge are restricted to applications where the workability of the concrete is not required, such as for residential pavements, sidewalks and stepping floors. |
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Revisão Chemical characterization and biotechnology applications of fungal glucans Silva, Maria de Lourdes Corradi da Martinez, Paula Felippe Izeli, Nataly Lino Silva, Iara Ribeiro Vasconcelos, Ana Flora Dalberto Cardoso, Marilsa de Stefani Stelutti, Rosângela Maria Giese, Ellen Cristine Barbosa, Aneli de Melo Abstract in English: This article gives an overview of exopolysaccharides produced by fungi. The structural characterization of beta-D-(1->3) and beta-D-(1->3, 1->6)- glucans is discussed focusing on different chemical and physical procedures. The industrial applications are also considered mainly from the point of view of human health. |
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Revisão Plant lipases from latex: properties and industrial applications Paques, Fernanda Wiermann Macedo, Gabriela Alves Abstract in English: Biocatalysts have innumerous advantages with respect to classical chemical processes, such as high specificity. Lipases (EC 3.1.1.3) are biocatalysts with large application in synthesis and hydrolysis reactions of triacylglycerols. The search for new sources of lipases has been intensified in the last years due to the high cost of microbial and animal lipases, wich restricts their use on an industrial scale. Lipases obtained from the latex of Carica papaya, Carica pentagona, Euphorbia characias, E. wulfenii, known for their proteolytic properties, are a good alternative source. In this review, we describe the well-known sources of vegetal lipases extracted from the latex and present some of their industrial applications. |
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Revisão Bioactive ceramics: state of the arts Andrade, Ângela Leão Domingues, Rosana Zacarias Abstract in English: Bioactive glasses undergo corrosion with leaching of alkaline ions when exposed to body fluids. This results in the spontaneous formation of a layer of hydroxyapatite (HA), the mineral component of natural bone, which in turn can induce bone growth in vivo. This paper describes the different types of bioactive glasses, the characterization methods currently used, and the main factors that influence their bioactivity. Nucleation and crystallization, the main mechanisms involved in the formation of hydroxyapatite, Ca10(PO4)6(OH)2, are discussed as a function of the chemical composition and the reactivity of the surface of the material. Finally, promising applications are considered. |
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Revisão Electroanalytical techniques for the determination of pesticides in foods Galli, Andressa De Souza, Djenaine Garbellini, Gustavo S. Coutinho, Cláudia F. B. Mazo, Luiz H. Avaca, Luis A. Machado, Sergio A. S. Abstract in English: The aim of this work is to discuss selected applications of electroanalytical techniques for the detection of pesticides in foods and beverages, published in the last ten years. The applications involved different working electrodes for the electroanalytical determination of pesticides, namely amperometric biosensors, cholinesterase-based biosensors, polymer-modified electrodes, ultramicroelectrodes and hanging mercury drop electrodes. They were used for several voltammetric and amperometric techniques in different analytical procedures for the detection and quantification of different classes of pesticides in different food matrices. |
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Divulgação Oxidative stress: relations between the formation of reactive species and the organism's defense Barreiros, André L. B. S. David, Jorge M. David, Juceni P. Abstract in English: This work describes the mechanism of action of some reactive oxygen species (ROS) and reactive nitrogen species (RNS) in the oxidative stress of the human body, and their consequences on damage to DNA, RNA, proteins and lipids. It also illustrates the defense system of our organism against these ROS and RNS species. The action of nonenzymatic protection systems is reported, with emphasis on micromolecules like Q10 coenzyme, vitamin C, alpha-tocopherol, carotenoids and flavonoids. The importance of flavonoids is also emphasized, and their body protection mechanism is detailed. |
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Divulgação Influence of colorants on the degradation and stabilization of polymers Saron, Clodoaldo Felisberti, Maria Isabel Abstract in English: Dyes and pigments are additives used in polymers to improve mainly the aesthetic properties of the material. However, the incorporation of these additives can directly affect polymer stability. The colorants can drastically decrease the lifetime and the performance of the material or can act as a stabilizer, improving significantly the stability of the polymer against degradation. Interaction between colorants and polymers is the cause of the stability changes. Some mechanisms are proposed to explain the action of colorants on polymers. However it is difficult to foresee this action without experiments. This work reviews the main mechanisms involved in the degradation and stabilization of polymers containing colorants. |
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Divulgação Nanodiamond films for applications in electrochemical systems and aeronautics and space technology Azevedo, Adriana Faria Ferreira, Neidenêi Gomes Abstract in English: The goal of this work is to show the use of undoped nanodiamond films as a new material for electrochemical and aerospace applications. Correlation between the applications and physico-chemical features of nano and conventional CVD polycrystalline diamond films are presented. An important and innovative application of these nanodiamonds is organic electrosynthesis, including pharmaceutical and water disinfection products, as well as electroanalytical applications, for example, development of biosensors for detection of glucose, glutamate and dopamine. In aeronautics and space developments, these nanodiamonds could be used as electrodes in rechargable batteries and in tribological investigations. |
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Divulgação Atomic force microscopy applied to immunoassays Ferreira, Antonio Aparecido Pupim Yamanaka, Hideko Abstract in English: Affinity reactions have been used for specific detection of their complementary partners and an enormous variety of enzyme-linked immunosorbent assay (ELISA) formats are used in research and in routine serological tests. With the advent of the atomic force microscopy (AFM) technique, the immune reactions have been monitored by these devices. In the present article we focus on applications of AFM to immunoassays. After introducing the basic concepts of AFM, a brief discussion on the monitoring of the interactions between antigens and antibodies through both topographic image and biosensor systems is presented. |
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Divulgação Two-dimensional correlation spectroscopy: fundamentals, applications and perspectives Pereira, Claudete Fernandes Pasquini, Celio Abstract in English: This paper presents the basic theory of generalized two-dimensional correlation spectroscopy. This method is applicable to various types of spectroscopy, including Infrared, Near Infrared and Raman Spectroscopy and it emphasizes spectral features not readily observable in conventional one-dimensional spectra. Some applications are cited, including work developed in Brazil. |
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Nota técnica Factorial design employed for microwave-assisted digestion of bean samples Costa, Letícia M. Korn, Maria das Graças A. Castro, Jacira T. Santos, Wagna P. C. Carvalho, Edivan V. Nogueira, Ana Rita A. Abstract in English: The use of factorial design was evaluated for optimization of focused-microwave-assisted digestion of bean samples. Calcium, Fe, Mg, Mn and Zn percentual recoveries were determined in digestates after focused-microwave-assisted digestion according to factorial design procedures. A cavity microwave digestion was carried out to certify the elemental compositions obtained. The accuracy was checked using a standard reference material, the NIST SRM 8433 - Corn Bran. Results are in agreement with certified values at the 95% confidence limit when the Student t-test was used. Volumes of nitric and sulfuric acid, temperature, and the interplay between HNO3 and H2SO4 initial volumes were significant variables according to P-values in the analysis of variance (ANOVA). |
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Nota técnica Direct determination of molybdenum in polyvitaminic tablets by voltammetry in non-aqueous media Almeida, Alex M. de Aleixo, Luiz M. Andrade, João Carlos de Coscione, Aline Renée Abstract in English: Adsorptive stripping voltammetry carried out in a homogeneous ternary solvent composed of N,N-dimethylformamide, water and ethanol, with alpha-benzoinoxime (alphaBO) as the complexing agent for Mo(VI) and a 0.5 mol L-1 acetic acid - sodium acetate buffer as supporting electrolyte was successfully used for the determination of molybdenum in polyvitamin-polymineral tablets. Tablet samples were analyzed and the results were compared with those obtained both by graphite furnace atomic absorption and by recovery tests, with good correlations, indicating that this may be considered as an alternative procedure for routine determination of Mo(VI) in pharmaceutical samples. |
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Nota técnica Atomic and molecular threshold photoelectron spectroscopy Lopes, Maria Cristina Andreolli Couto, Helder Moreira, Cleber Dias Silva, Helen Abstract in English: A threshold photoelectron spectrometer applied to the study of atomic and molecular threshold photoionization processes is described. The spectrometer has been used in conjunction with a toroidal grating monochromator at the National Synchrotron Radiation Laboratory (LNLS), Brazil. It can be tuned to accept threshold electrons (< 20 meV) and work with a power resolution of 716 (~18 meV at 12 eV) with a high signal/noise ratio. The performance of this apparatus and some characteristics of the TGM (Toroidal Grating Monochromator) beam line of LNLS are described and discussed by means of argon, O2 and N2 threshold photoelectron spectra. |
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Nota técnica Simulation of complex splittings of ¹H NMR spectra Constantino, Mauricio Gomes Silva, Gil Valdo José da Heleno, Vladimir Constantino Gomes Borin, Ivana Aparecida Campos, Ivan P. de Arruda Abstract in English: Complex ¹H NMR spectra multiplets that cannot be easily understood by simple inspection are rather frequent in the daily work of the organic chemistry analyst. The multiple and excellent new techniques available from modern instruments usually provide satisfactory solutions, but there are still many cases where a simulation is necessary, at least to obtain a final confirmation. It is extremely convincing to see that a graph, obtained by calculations with chemical-shift and coupling-constant values only, can be virtually identical to the experimental spectrum. This paper describes a computer program to make such calculations. The program is free and can be downloaded from <A HREF="http://artemis.ffclrp.usp.br/NMR.htm">http://artemis.ffclrp.usp.br/NMR.htm</A> (click on SimEsp_NMR_Compil.zip). All routines are also available and may be used without any restrictions. The paper includes a fairly detailed discussion about how the calculations are made. |
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Educação The importance of Qualitative Analytical Chemistry in Chemistry courses in Brazilian universities Alvim, Terezinha Ribeiro Andrade, João Carlos de Abstract in English: The results of a survey of institutions offering undergraduate studies, with the objective of evaluating the importance of Qualitative Analytical Chemistry for Chemistry courses in Brazil, are presented and discussed. Judging by the data, the content of the course of Qualitative Analytical Chemistry is considered by the Brazilian institutions offering undergraduate studies to be a body of knowledge essential for the formation of the chemist. This aspect is deemed valid for both baccalaureate and teaching license studies. |
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Educação The Chemistry show: motivating the scientific interest Arroio, Agnaldo Honório, Káthia M. Weber, Karen C. Homem-de-Mello, Paula Gambardella, Maria Teresa do Prado Silva, Albérico B. F. da Abstract in English: The aim of this article is to provide the understanding of the chemical world that underlies everything around us by introducing basic chemical concepts and their everyday applications. The specific topics presented were selected according to their relevance and their ability to be presented as an exhibition. This format is based on the visual effects that help the public to see abstract descriptions in a concrete form. In addition, a soundtrack is used to stimulate the affective intelligence and relax the public. According to the results obtained here, we can conclude that chemical demonstrations, combined with music, help the presentation of scientific topics and motivate and facilitate the "chemistry communication". |
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