Utilização de índices r e R obtidos de programas interlaboratoriais para o controle de precisão de método analítico: Determinação de água por Karl Fischer

Values of repeatability (r) and reproducibility (R) are parameters of an analytical method. They are related to the maximum difference between two results of analysis (permissible range) and can be obtained by interlaboratorial comparisons. They represent great importance for the quality control of the results and decisions about the fitness-for-purpose of the method. Water determination in fuel oil samples were performed by 16 laboratories, using the Karl Fischer reaction, during the period from June 1997 to December 1999. Values of r and R were presented. Discussion is made in terms of the main factors that would be contribution to analytical method variabilities and uncertainties of final results.

Parâmetros termodinâmicos da reação de adsorção de boro em solos tropicais altamente intemperizados

The driving force of boron adsorption on some tropical soils was evaluated by means of thermodynamic parameters. The batch method was employed, and the reaction was monitored at different pH values. The Langmuir equation successfully fitted the experimental results and provided reasonable isotherm parameters. Boron adsorption increased as a function of the pH of the soil solution and the concentration of added boron. The reaction was favorable and proceeded spontaneously, being strongly exoergic, as indicated by a negative free energy (deltaG) and a separation factor (K R) < 1. The boron adsorption phenomenon and the soil-solution interface were thermodinamically described using a theoretical model.

Fotoquímica de alfa,alfa-dimetilvalerofenona adsorvida em celulose microcristalina

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.

Polímeros biodegradáveis - uma solução parcial para diminuir a quantidade dos resíduos plásticos

The large use of plastics has generated a waste deposit problem. Today plastic wastes represent 20% in volume of the total waste in the municipal landfills. To solve the disposal problem of plastics methods have been employed such as incineration, recycling, landfill disposal, biodegradation and the use of biodegradable polymers. Incineration of plastic wastes provokes pollution due to the production of poisonous gases. Recycling is important to reduce final costs of plastic materials, but is not enough in face of the amount of discarded plastic. In landfills plastic wastes remain undegraded for a long time, causing space and pollution problems. Biodegradation is a feasible method to treat some plastics, but intensive research is necessary to find conditions for the action of microorganisms. All of these methods are important and the practical application of each one depends on the type and amount of the plastic wastes and the environmental conditions. Therefore, a great deal of research has focused on developing biodegradable plastics and its application because it is an important way for minimizing the effect of the large volume of plastic waste discarded in the world.

Estratégias utilizadas no combate a resistência bacteriana

This article provides an overview on the recent achievements to combat Gram-positive bacteria and the mechanisms related to antimicrobial activity and bacterial resistance. Selected synthetic methodologies to access structurally diverse bioactive compounds are presented in order to emphasize the most important substances currently developed to overcome multiresistant strains. The main properties of vancomycin and related glycopeptide antibiotics are also discussed as a background to understanding the design of new chemotherapeutic agents.

Alquilbenzeno sulfonato linear: uma abordagem ambiental e analítica

The environmental impact of detergents and other consumer products is behind the continued interest in the chemistry of the surfactants used. Of these, linear alkylbenzene sulfonates (LASs) are most widely employed in detergent formulations. The precursors to LASs are linear alkylbenzenes (LABs). There is also interest in the chemistry of these hydrocarbons, because they are usually present in commercial LASs (due to incomplete sulfonation), or form as one of their degradation products. Additionally, they may be employed as molecular tracers of domestic waste in the aquatic environment. The following aspects are covered in the present review: The chemistry of surfactants, in particular LAS; environmental impact of the production of LAS; environmental and toxicological effects of LAS; mechanisms of removal of LAS in the environment, and methods for monitoring LAS and LAB, the latter in domestic wastes. Classical and novel analytical methods employed for the determination of LAS and LAB are discussed in detail, and a brief comment on detergents in Brazil is given.

A reatividade do estado excitado triplete de 1,3-indanodiona em benzeno

Rate constants for the quenching of 1,3-indandione (1) triplet by olefins and by hydrogen and electron donors were obtained employing the laser flash photolysis technique in benzene solution. These rate constants ranged from 2.5x10(5) Lmol-1s-1 (for 2-propanol) to 5.9x10(9) Lmol-1s-1 (for DABCO). From the quenching rate constants by 1,3-cyclohexadiene, trans- and cis-stilbene a value between 49.3 and 52.4 kcal/mol was estimated for the energy of the triplet state of 1,3-indandione. The npi* character of this triplet state was evidenced by the quenching rate constants obtained when typical hydrogen donors were employed as quenchers. For 2-phenyl-1,3-indandione (2, R=phenyl) a fast Norrish type I reaction is operating which prevents the determination of kinetic and spectroscopic data of its triplet state.

Métodos de extração para quantificação de manganês disponível em fertilizantes

The solubility of Mn in different fertilizers (MnSO4.H2O-p.a., MnO2-p.a.+MnO-Ind., MnO2-Ind.+MnO-Ind., MnO2-p.a., MnO2-Ind. and MnO-Ind.) was determined using different methodologies: total content and soluble contents in water, 10% H2SO4, citric acid at 20 g L-1, diluted neutral ammonium citrate, (1+9) and DTPA at 0.005 mol L-1. The Mn solubilities in the latter three extractors were assessed after agitation of the sample for one hour and after boiling for 5 minutes. The extraction procedure using neutral ammonium citrate (1+9), at 1:100, with agitation for one hour, was shown to be the most adequate to assess the availability of Mn in fertilizers.

Constituintes químicos das flores de Pterogyne nitens (Caesalpinioideae)

The phytochemical investigation of the flowers of Pterogyne nitens (Caesalpinioideae) resulted in the isolation and identification of nine phenolic derivatives, quercetin 3-O-sophoroside, taxifolin, astilbin, ourateacatechin, caffeic, ferulic, sinapic, chlorogenic and gallic acid, besides two guanidine alkaloids, pterogynine, pterogynidine. This is the first time these compounds have been reported in P. nitens flowers. As this is a monospecific genus, these secondary metabolites may have taxonomical significance. Their structures were assigned on the basis of spectroscopic analyses, including two-dimensional NMR techniques.

Validação de métodos para determinação de fluoxetina em cápsulas

A UV spectrophotometric method was developed and validated and a chromatographic method was adapted from the American Pharmacopeia for the analysis of Fluoxetine Hydrochloride capsules. Ethanol was used as solvent for the spectrophotometric method, with detection and determination at 276 nm. The separation for the chromatographic method was carried out using the reversed-phase column LC-8, triethylamine buffer, stabilizer free tetrahydrofuran and methanol (5:3.5:1.5), pH 6.0 as mobile phase and detection at 227 nm. The results obtained for both methods showed to be accurate, precise, robust and linear over the concentration range 100.00 - 300.00 µg/mL and 40.00 - 80.00 µg/mL of fluoxetine hydrochloride for the spectrophotometric and chromatographic methods, respectively. The accuracy of the methods was evaluated by a recovery test and showed results between 98.89 and 101.10%.

Desempenho físico-químico e mecânico de concreto de cimento Portland com borracha de estireno-butadieno reciclada de pneus

Physicochemical and mechanical techniques were carried out to characterize three concrete tyre-rubber waste dosages such as 5, 10 and 15%, w/w. The elastomeric material was identified as styrene-butadiene rubber (SBR). It was observed that the growing SBR content in the mixture decreased the concrete performance. The best results were presented by 5% w/w tyre-rubber waste concrete sample. This composition was tested at Mourão hydroelectric powerplant spillway as repairing material.

Heterogeneidade de álcoois secundários em aguardentes brasileiras de diversas origens e processos de fabricação

Secondary alcohol concentrations in sugar cane spirits from different origins were determined by gas chromatography. A great variation in the concentration of the secondary alcohols was found in these spirits. Of the 33 brands analyzed, 8 of them were found to be out of conformity with the legislation. Sec butanol, for which the maximum allowed concentration level is 100 mg.L-1 in absolute ethanol, was found within a concentration range between 5 mg.L-1, the limit of quantitation (LQ) and 408 mg.L-1 in absolute ethanol. Sugar cane samples from Salinas, MG, were the only ones that exhibited self similarity because of the low concentrations of n-butanol and n-amylic alcohol (< limit of detection LD).

Estudo da reatividade do estado excitado triplete de 1,4-diaza-9-fluorenonas frente a doadores de hidrogênio e de elétron

The effect of the introduction of nitrogen atoms upon the triplet excited state reactivity of 1,4-diaza-9-fluorenone (1) and 1,4-diaza-9-benz[b]fluorenone (2), in acetonitrile, was investigated employing the nanosecond laser flash photolysis technique. The intersystem crossing quantum yield (Φces) for 1 and 2 was determined using 9-fluorenone as a secondary standard (Φces= 0.48, in acetonitrile) and for both diazafluorenones a value of Φces= 0.28 was found. Quenching rate constants ranged from 8.17x10(4) L mol-1 s-1 (2-propanol) to 1.02x10(10) L mol-1 s-1 (DABCO) for 1,4-diaza-9-fluorenone and from 6.95x10(5) L mol-1 s-1 (2-propanol) to 5.94x10(9) L mol-1 s-1 (DABCO) for 1,4-diaza-9-benz[b]fluorenone, depending if the quenching process involves energy, hydrogen or electron transfer. A comparison between quenching rate constants for both diazaflurenones and the parent compound, i.e. 9-fluorenone, a ketone with lowest triple state of ππ* configuration, lead to the conclusion that the reactive triplet excited state for 1,4-diaza-9-fluorenone and 1,4-diaza-9-benz[b]fluorenone has ππ* configuration.

Líquido iônico [bmim.PF6] como solvente: um meio conveniente para estudos por fotólise por pulso de laser

The spectroscopic behavior of thioxanthone and benzil (diphenylethanedione or dibenzoyl) in the ionic liquid [bmim.PF6] has been investigated employing the laser flash photolysis technique. Triplet-triplet absorption spectra for these carbonyl compounds in [bmim.PF6] are similar to those observed in organic solvents. The triplet lifetime for thioxanthone in desogygenated samples is very long (71 μs), whereas in oxygen-saturated solution is 500 ns, which indicates the low oxygen solubility in this solvent. For benzil, lifetimes of 10 μs in [bmim.PF6] and 3.8 μs in acetonitrile were obtained. The decay for triplet thioxanthone and benzil follows a clear first order kinetics in [bmim.PF6], from which one can conclude that triplet-triplet annihilation is not an important decay process in this solvent.

Síntese de regioisômeros quirais a partir de D-manitol: obtenção de uma mistura de álcoois acetilênicos

The synthesis of chiral acetylenic regioisomers was described by using an appropriate intermediate such as isopropylidene glycerol, a synthon widely used in the enantioselective syntheses. This intermediate was prepared from D-mannitol. The nine obtained compounds have been characterized by their respective spectral data. The mixture of chiral acetylenic alcohols showed activity against Escherichia coli when tested through the monitoring of CO2 released during microbial respiration by using a conductimetric system.