Resumo em Inglês:

The influence of acidity on the synthesis and redox behavior of polypyrrole films was studied using galvanostatic and potentiodynamic techniques employing aqueous solutions formed by H2SO4/Na2SO4 , HCl/NaCl and HCl/CsCl. The chemical structure of the films were investigated using the FTIR technique. The polymer behavior as a function of the pH used in the cyclic voltammetric measurements is explained in terms of the mechanism responsible for the charge compensation formed during the polymer chain oxidation. From the FTIR measurements, it is seen that the water nucleophilic attack during the synthesis, does not occur under the experimental conditions employed in this work.

Resumo em Inglês:

The hexane and methanolic extracts from pheromonal glands of Castnia licus (Drury) virgin females have been studied. Analyses by gas chromatography and mass spectrometry allowed us to determine the major constituents present in the hexane extract as n-alkanes C21 to C30, (Z)-9-hexadecenoic acid (C16), and (Z)-9-octadecenoic acid (C18) and hexadecanoic acid (C16). Aldehyds, alkenes and acetates were also detected in low concentrations in the extracts. Female pheromone glands were analysed for pheromone precursors using the methanolic extract. In addition to the compounds methyl hexadecanoate and methyl (Z)-9-octadecenoate, the glandular tissue contains a homologous series of methyl esters from C12 to C24. The hexane extract of the female abdomenal glands elicited activity from males in a behavioural bioassay.

Resumo em Inglês:

Montmorillonite clay from Brazil was pillared with aluminium polyhydroxications. The influence of Al/Mont ratio and calcination temperature in the properties of the prepared materials was studied. Results showed that the pillarization process increases the basal spaces of the natural clay from 9,7 to 18,5Å and the superficial area from 41 to ~230m2/g. The calcination process at different temperatures showed that the pillared material was stable until 600oC but the adequate temperature for calcination was 450oC. Materials prepared with different Al/Mont ratios showed the maximum Al incorporation for ratios >10meq Al/g and a good distribution for rations >15meq Al/g.

Resumo em Inglês:

Phytochemical investigation of the fruits of Rheedia gardneriana led to the isolation of sesquiterpenes mixture, methyl esters of fatty acids (palmitate, estearate, oleate, linoleate, linolenate), sugars (galactose, glucose, fructose), triterpene (oleanolic acid), steroids mixture (stigmasterol and sitosterol) and the new tetraprenylated benzophenone 7-epiclusianone.

Resumo em Inglês:

Potentiometric amalgam electrodes of lead, cadmium, and zinc are proposed to study the complexation properties of commercial and river sediment humic acids. The copper complexation properties of both humic acids were studied in parallel using the solid membrane copper ion-selective electrode (Cu-ISE). The complexing capacity and the averaged conditional stability constants were determined at pH 6.00 ± 0.05 in medium of 2x10-2 mol L-1 sodium nitrate, using the Scatchard method. The lead and cadmium amalgam electrodes presented a Nernstian behavior from 1x10-5 to 1x10-3 moles L-1 of total metal concentration, permitting to perform the complexation studies using humic acid concentrations around of 20 to 30 mg L-1, that avoids colloidal aggregation. The zinc amalgam electrode showed a subnernstian linear response in the same range of metal concentrations. The Scatchard graphs for both humic acids suggested two classes of binding sites for lead and copper and one class of binding site for zinc and cadmium.

Resumo em Inglês:

210Po concentrations have been determined in one green alga and in five freshwater plants grown in a pond of the Carapebus restinga (State of Rio de Janeiro). The alga Chara sp showed elevated concentration of 210Po, similar to that observed for marine algae. All the other plants had the lowest concentration of 210Po in the stems and the highest in the roots. Intermediate values were observed in the leaves. The unexpected high concentration of 210Po in the roots, even superior to reported values for roots of plants from high radioactive background areas, must be due to the elevated levels of this radionuclide in associated soils that are known to be rich in humic organic material. There seem to have been no translocation of this radionuclide from the roots to the other parts of the plants.

Resumo em Inglês:

An on-line electrodissolution procedure implemented in a flow injection system for determination of copper, zinc and lead in brasses alloys by ICP-AES is described. Sample dissolution procedure was carried out by using a PTFE chamber and a DC power supply with constant current. Solid sample was attached to chamber as anode and a gold tubing coupled in the chamber was used as cathode. An electrolytic solution flowing through the gold tubing closed the electric circuit with sample, in order to provide condition for electric dissolution when the DC power supply was switched on. The best results were achieved by using a 1.5 mol l-1 nitric acid solution as electrolyte and a 2.5 A current intensity. The procedure presented a good performance characterized by a relative standard deviation better than < 5% (n=5) and a sample throughput of 180 determinations per hour for Cu, Zn and Pb. Results were in agreement with those obtained by conventional acid dissolution (99% confidence level).

Resumo em Inglês:

The influence of the presence of hydrogen on Pt/TiO2 catalysts submitted to reduction treatment has been studied by FT-IR at room temperature. After submitting to LTR treatment, the hydrogen spillover has been detected and the presence of hydrogen at the bulk is shown to produce a strong absorption in the infrared spectral region. After HTR treatment, the hydrogen is strongly chemissorbed.

Resumo em Inglês:

A method is described for recovering and purifying 241Am from lightning-conductors and smoke detectors. The method is based on the precipitation of silver, as AgCl, the main impurity, and extraction of americium with TBP. Further purification with ion-exchange resin is also used. The results have shown that by this method the americium is obtained with high purity.

Resumo em Inglês:

Acid base properties of mixed species of the microalgae Spirulina were studied by potentiometric titration in medium of 0.01 and 0.10 mols L-1 NaNO3 at 25.0±0.10 C using modified Gran functions or nonlinear regression techniques for data fitting. The discrete site distribution model was used, permitting the characterization of five classes of ionizable sites in both ionic media. This fact suggests that the chemical heterogeneity of the ionizable sites on the cell surface plays a major role on the acid-base properties of the suspension in comparison to electrostatic effects due to charge-charge interactions. The total of ionizable sites were 1.75±0.10 and 1.86±0.20 mmolsg-1 in ionic media of 0.01 and 0.10 mols L-1 NaNO3, respectively. A major contribution of carboxylic groups was observed with an average 34 and 22% of ionizable sites being titrated with conditional pcKa of 4.0 and 5.4, respectively. The remaining 44% of ionizable sites were divided in three classes with averaged conditional pcKa of 6.9, 8.7 and 10.12, which may be assigned respectively to imidazolic, aminic, and phenolic functionalities.

Resumo em Inglês:

We analyse vibrational frequencies of 168 compounds with the AM1 model concerning its experimentally observed gaseous frequencies. Stretching of CH, NH, OH and CO bonds, its related bending frequencies, and the CC frame movements are the studied vibrations. The results show problems with the AM1 vibrational splittings. Often symmetric stretching frequencies, like in CH3, CH2 and NH3, appear switched with the corresponding antisymmetrical ones. Among the studied vibrations many stretchings are overestimated, while bendings oscillate around experimental values. Fluorine stretchings, NN, OO, CH, double and triples CC bonds and cyclic hydrocarbon breathing modes are always overestimated while torsions, umbrella modes and OH/SH stretching are, in average, underestimated. Graphical analysis show that compounds with the lowest molecular masses are the ones with the largest difference to the experimental values. From our results it is not possible to fit confortably the calculated frequencies by a simple linear relationship of the type, n(obs)=a*n(AM1). Better aggreement is obtained when different curves are adjusted for the stretching and bending modes, and when a complete linear function is used. Among our studies the best obtained statistical results are for CH, NH and OH. The conclusions obtained in this work will improve the AM1 calculated frequencies leading to accurate results for these properties.

Resumo em Inglês:

The structure of several types of layered materials will be described. These include clays, layered double hydroxides, group IV metal phosphates and other layered materials. The preparation of the pillared materials and pillaring agents will be presented along with a description of the properties and applications of the products.

Resumo em Inglês:

The Michael addition reaction has been reported as a conventional nucleophilic process. However, more recently, alternative mechanisms involving electron transfer between acceptor and donnor species have been proposed.

Resumo em Inglês:

The peroxyoxalate system is still one of the most efficient chemiluminescence reactions and the only one supposed to involve the "Chemically Initiated Electron Exchange Luminescence - CIEEL" mechanism, with proved high efficiency. Besides the academic interest in the elucidation of the mechanism of this complex reaction, the peroxyoxalate system has found a variety of applications in analytical chemistry. This review contains (i) a short introduction to basic concepts in chemiluminescence, (ii) a critical summary of mechanistic studies on the peroxyoxalate reaction, (iii) and some examples of analytical applications. Although there are some recent reviews on chemiluminescence, no specific critical revision on mechanistic and analytical features of the peroxyoxalate system has been published.

Resumo em Inglês:

The aim of this work is to present a tutorial on Multivariate Calibration, a tool which is nowadays necessary in basically most laboratories but very often misused. The basic concepts of preprocessing, principal component analysis (PCA), principal component regression (PCR) and partial least squares (PLS) are given. The two basic steps on any calibration procedure: model building and validation are fully discussed. The concepts of cross validation (to determine the number of factors to be used in the model), leverage and studentized residuals (to detect outliers) for the validation step are given. The whole calibration procedure is illustrated using spectra recorded for ternary mixtures of 2,4,6 trinitrophenolate, 2,4 dinitrophenolate and 2,5 dinitrophenolate followed by the concentration prediction of these three chemical species during a diffusion experiment through a hydrophobic liquid membrane. MATLAB software is used for numerical calculations. Most of the commands for the analysis are provided in order to allow a non-specialist to follow step by step the analysis.

Resumo em Inglês:

The infrared (IR) spectra of the four distict conformers located on the multidimensional potential energy surface (PES) for the 3-phenyl-1,2,3-oxathiazolidine 2-oxide compound have been calculated using the semiempirical quantum-mechanical method PM3. The band spectra are reported and compared directly with the experimental spectrum. The IR intensities are shown to be much more sensitive to conformational changes than the vibrational frequencies and so, the theoretical analysis of the IR spectrum can be used as a tool for helping in the elucidation of the structure of heterocyclic compounds.

Resumo em Inglês:

In this article are presented some fundamental elements of the conventional and of the variational transition state theories which are needed to carried out calculations of semi-classical chemical dynamics. Some important bottlenecks in building reliable potential energy surfaces using electronic structure calculations are also discussed. It is put emphasis on the methodology of the variational transition state theory with interpolated corrections (VTST-IC), and its application in the calculations of the rate constants and of the kinetic isotope effect (KIE) of CH4 + Cl <FONT FACE="Symbol">«</font> CH3 + HCl reaction.

Resumo em Inglês:

In this paper we describe the results of a research effort developed in Laboratório de Avaliação e Síntese de Substancias Bioativas (LASSBio, UFRJ) in the utilization of Brazilian abundant natural product, safrole (1), the principal chemical constituent of Sassafras oil (Ocotea pretiosa), as an attractive synthon to access different chemical class of bioactive compounds, as prostaglandins analogues, non-steroidal antiinflammatory agents and antithrombotic compounds.

Resumo em Inglês:

This paper describes in detail a technique employed to grow quasi-spherical single crystals of noble metals for electrochemical applications, using platinum as an example. The metal beads were formed by melting the extremity of a wire in an oxygen / butane flame. X-ray techniques were used to check the crystallization and to determine the orientation of the crystals. Treatment with a pure hydrogen flame followed by a cooling procedure in a hydrogen / argon atmosphere were used for conditioning the well-defined platinum single crystal surfaces. Finally, electrochemical characterization of the Pt(111), Pt(110) and Pt(100) surfaces was done in diluted sulfuric acid solution in the hydrogen adsorption / desorption potential region.

Resumo em Inglês:

In this study we describe an experimental procedure based on a chemical industrial process of soya-bean oil extraction applied in general chemistry for undergraduate students. The experiment was planned according to the Science, Technology and Society (STS) approach to teach basic chemical concepts and provide grounding in the management of environmental care. The use of real life chemistry problems seems to salient the relevance of chemistry to our students and enhances their motivation to learn both the practical and theoretical components of the discipline.

Resumo em Inglês:

The names of the chemical elements in Brazilian portuguese are presented, including a discussion of corresponding Brazilian nomenclature rules and translation of some parts of the pertinent IUPAC rules. The rules for naming groups of elements in the periodic table, as well as those for the symbolic indication of atomic number, mass number and electric charge of atoms, are also presented.