Estudo ab-initio da a-alanina em meio aquoso

Ab initio Hartree-Fock (HF), Density Functional (B3LYP) and electron correlation (MP2) methods have been used to caracterize the aqueous medium intramolecular hydrogen bond in a-alanine. The 6-31G* and 6-31++G** were taken from Gaussian94 library. We were concerned on the structure of three conformers of a-alanine, in their neutral form plus on the structure of the zwitterionic form (Z). The Z structure is a stationary point at the HF/6-31G* level but it is not when diffuse functions and electron correlation are included. This results shows that the Z form does not exist in the gas phase. The inclusion of solvent effects changed significantly the results obtained in gas phase, therefore this inclusion make the Z form a stationary point within all level of theory, and the relative energy depends dramatically on the level of calculation.

Termodinâmica estatística de líquidos com o método de Monte Carlo. II. O líquido clorofórmio

Thermodynamic properties and radial distribution functions for liquid chloroform were calculated using the Monte Carlo method implemented with Metropolis algorithm in the NpT ensemble at 298 K and 1 atm. A five site model was developed to represent the chloroform molecules. A force field composed by Lennard-Jones and Coulomb potential functions was used to calculate the intermolecular energy. The partial charges needed to represent the Coulombic interactions were obtained from quantum chemical ab initio calculations. The Lennard-Jones parameters were adjusted to reproduce experimental values for density and enthalpy of vaporization for pure liquid. All thermodynamic results are in excelent agreement with experimental data. The correlation functions calculated are in good accordance with theoretical results avaliable in the literature. The free energy for solvating one chloroform molecule into its own liquid at 298 K and 1 atm was computed as an additional test of the potential model. The result obtained compares well with the experimental value. The medium effects on cis/trans convertion of a hypotetical solute in water TIP4P and chloroform solvents were also accomplished. The results obtained from this investigation are in agreement with estimates of the continuous theory of solvation.

Influência da acidez do meio sobre a síntese e o comportamento redox do polipirrol

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.

Reações orgânicas em meio aquoso

The use of water as solvent in organic reactions has been uncommon for several reasons, among them the low solubility of the reactants, the incompatibility of the intermediates with water, and the competition between the desired reaction and hydrolysis. Breslow in 1980, demonstrated that the hydrophobic effect accelerates Diels-Alder reactions and gives a high endo/exo selectivity. Since then, many other reactions were studied in this medium, and below we show the principal results. Besides the academic interest, human and economic aspects are included in this study. Water as a solvent minimizes environmental impact, costs and increases operational safety.

Influência do meio reacional no comportamento fotoquímico do inseticida paration etílico

The photodegradation of parathion in natural and dezionised waters was studied under irradiation at two different wavelengths: 280 nm and 313 nm. The influence of humic acids was evaluated. The results demonstrated that the degradation occurred only due to photochemical processes. The chemical hydrolysis and biological processes can be neglected in this case. The addition of humic acids did not increase the photodegradation rate in either water samples (natural or dezionised). In alkaline solutions the photodegradation rate was higher in dezionised water when compared to natural waters. The kinetic degradation in all experiments obeyed a first order reaction pattern.

Efeito da concentração do catalisador acetilacetonato férrico na cura de poliuretano à base de polibutadieno líquido hidroxilado (PBLH) e diisocianato de isoforona (IPDI)

The reaction between hydroxy-terminated polybutadiene and isophorone diisocyanate constitutes the base of the curing process of the most composite solid propellant used in the propulsion of solid rocket propellant. In this work, differential scanning calorimetry and viscosity measurements were used to evaluate the effect of the ferric acetylacetonate catalyst concentration on the reaction between HTBR and IPDI. These analyses show one exotherm, which shifts to lower temperatures as the catalyst concentration increases. The viscosity analyses show that the increase of temperature causes, at first, a reduction in the mixture viscosity, reaching a minimum range called gelification region (increasing the crosslinking density).

Estudo da degradação do herbicida ácido 2,4- diclorofenoxiacético (2,4-D) por meio da radiação gama do cobalto-60 em solução aquosa contendo ácido húmico

The use of pesticides in agriculture presents some problems to ecosytems as a consequence of their remaining in the environment. Conventional methods for environmental decontamination sometimes just transfer these residues from one place to another. The use of gamma radiation from cobalt-60 to induce 2,4-D degradation in aqueous solution containing humic acid was studied. Results show that the herbicide is completely degraded after treatment with a 30 kGy dose. There were decreases in the degradation of the 2,4-D when humic acid was added at all doses. Some radiolytic products are proposed. The 2,4-D radiolytic yields (G) from 2,4-D were calculated.

Estudos de proteção da célula de saccharomyces cerevisiae para utilização em reações de redução em meio orgânico

New methodologies for protection of Saccharomyces cerevisiae (FP) cells when supported in montmorillonite K10 (K10), recovered or not with gelatin (G) and in the presence or absence of sucrose (S) are presented. These systems were used for the enantioselective reduction of ethyl acetoacetate and a-chloroacetophenone in hexane, under FP/K10/G/S and FP/S at 20ºC during 24 hours, affording S-(+)-ethyl-3-hydroxybutanoate in 100% conversion and 99% ee, and R-(-)-2-chloro-1-phenylethanol 79% and 78% ee at 20 and 30 ºC, respectivelly.

Pré-concentração de chumbo e cádmio em um sistema de micro extração líquido-líquido e determinação por espectrometria de absorção atômica com chama

A method for determination of lead and cadmium in aqueous samples using solvent microextraction and dithizone as complexing agent with FAAS was developed. Solvent microextraction parameters were optimized. The effect of foreign ions on the extraction yields was studied. The extraction was carried out until the aqueous to organic phase ratio achieved a 250 fold preconcentration of metals. For preconcentration times of 4 min the 3sigma detection limits, relative standard deviations (n=7) and linear calibration ranges were 1.6 mug L-1, 5.8% and 10.0 -- 80.0 mug L-1 for lead and 11.1 ng L-1, 5.9% and 0.3 -- 3.0 mug L-1 for cadmium, respectively. The solvent microextraction procedure presented here was applied to the determination of lead and cadmium in natural waters.

Sistema de alimentação gás-líquido para medidas de atividade catalítica

This note has as objective to present the advantages of the use of syringe-type pumps for the feeding of liquid reactants, together with mass flow controllers for gases, instead of the saturators, as it is generally accomplished. Among the advantages, the system with syringe pumps presents a greater flexibility in flow control as well as in composition compared with the system that uses saturator. In addition, the flow of the liquid reactants is known with precision in the syringe pump system.

Fármacos no meio ambiente

Pharmaceutical drugs have been detected in sewage treatment plants, surface waters, underground waters and potable waters. Some investigations have been conducted in several countries such as Germany, Brazil, Canada, United States, The Netherlands, England and Italy. Patients and animals excrete part of pharmaceuticals used for human and veterinary medicine after administration in domestic sewage or on the soil. Drugs residues which have not been completely removed during passage through a sewage treatment plant (STP) enter the aquatic environment. The effects of such residual drugs in terrestrial and aquatic organisms are scarcely known.

Determinação da 2,5-hexanodiona em amostras de urina submetidas à hidrólise ácida: importância da coluna cromatográfica e do pH do meio

Acidic hydrolysis of samples is frequent in urinary 2,5-hexanodione determination. This hydrolysis should be performed under proper conditions, in order to avoid interference, such as the presence of 2,5-dimethylfurane and 2-acetylfurane. The results of the present work, as well as data from the literature, show that the use of non-polar or slightly polar chromatographic columns of 30 m length is an essential condition for 2,5-HD determination in an acid hydrolysed urine sample. In the same way the pH should be kept between 0.3 and 0.5. The mean concentrations of 2,5-HD in samples submitted to hydrolysis (0.50 ± 0.28 mg/g of creatinine) was about 3 times higher than those found in the samples without acid hydrolysis (0.19 ± 0.3 mg/g of creatinine).

Efeito do polietilenoglicol e da albumina na imobilização de lipase microbiana e na catálise em meio orgânico

Poly (ethylene) glycol (PEG) and bovine serum albumin (BSA), as additive agents, were used to enhance the activity of immobilized microbial lipase in organic solvent. Controlled pore silica (CPS) was selected as matrix and different immobilization procedures were evaluated: directly lipase binding on CPS and simultaneous addition of lipase and additive agent on the same support. The highest coupling yield (59.6%) was attained when the immobilization procedure was performed at lipase loading of 150 U/g support in the presence of PEG-1.500. This immobilized system was used in esterification reactions under repeated batch cycles and the biocatalyst half-life was found to increase 2.7 times when compared with the control.

Identificação de resíduos de disparos de armas de fogo por meio da técnica de espectrometria de massas de alta resolução com fonte de plasma indutivo

The violence derived from crimes involving firearms represents one of the main concerns of society. For this reason modern techniques have emerged in forensic science to identify suspects at crime scenes. This work describes a methodology to identify residues present in the hands of suspect by using a high resolution inductively coupled plasma mass spectrometry and collection procedure based on ethylenediaminetetraacetic acid (EDTA) solution as a complexing agent in moistened swabs. In order to distinguish real gunshot residues from others types of residues present in the hand of suspect, ternary ratio per cent diagrams were developed for antimony (Sb), barium (Ba) and lead (Pb) detected on the hands of volunteers, before and immediately after shooting tests, revealing a remarkable difference in both situations.

Extração de Al(III), Cr(III) e Fe(III) de meio etanólico usando o xerogel anilinapropilsílica

In this study, the preparation of the xerogel anilinepropylsilica is reported. The ability of the xerogel for extracting Al(III), Cr(III) and Fe(III) from ethanol was investigated at 25 ºC. The xerogel adsorption capacities were obtained from the adsorption isotherms by using the batch method. Flame atomic absorption spectrometry (FAAS) was used to estimate the concentration of metal ions in solution. The adsorption affinity follows the series Cr(III) > Fe(III) > Al(III) and the maximum adsorption capacities of the metal ions were 0.61, 0.52 and 0.43 mmol g-1, respectively.