Rapid determination of PAHs in soil samples by HPLC with fluorimetric detection following sonication extraction

A rapid method for the determination of PAHs in soil samples based on their extraction with methylene chloride by sonication and subsequent separation by HPLC with fluorimetric detection is proposed. A Hypersil Green PAH column was used with a gradient of acetonitrile/water as the mobile phase, together with a program of nine excitation and emission wavelength pairs. Recoveries were in the range 70-98%, except for acenaphthene and naphthalene, at concentration levels 1.08-442 microg/kg with relative standard deviations in the range 2-15% (n = 4). Total PAHs found in soil samples were in the range 15-282 microg/kg. The results were compared with those obtained by applying the 3540 EPA method for two samples.     

Natural radioactivity of building materials

Experiments were designed to measure trace uranium concentration and the rate of radon exhalation from masonry structural materials, both bare and surface finished and coated. LR115 cellulose nitrate track detectors were used to record the alpha emission from structural material surface. Fission track, neutron activation and fluorometric analysis methods were used to determine the uranium content. Most types of paints studied will reduce alpha contribution and radon emanation from building materials.     

A fluorimetric study of pindolol and its complexes with cyclodextrins

Spectrofluorimetric characteristics of pindolol have been investigated with the aim of using this technique for analytical determinations. Other monosubstituted indole derivatives, 4-methoxy and 5-methoxyindole, have been also studied for comparative purposes. Corrected excitation and emission wavelengths in different solvents are reported and the effect of solvent on the Stokes shifts of these compounds has been analysed using the Lippert equation. In addition, the Stokes shift of pindolol has been determined in dioxan-water solvent mixtures and the presence of specific solvent effects is discussed. The fluorescence of pindolol is pH dependent, the quantum yields determined in water are lower than those in other solvents. With respect to the sensitivity, it has been found that the detection limits in aqueous solutions are improved in the presence of beta and methyl-beta-cyclodextrin. Finally, a fluorimetric analysis of the interaction between pindolol and different cyclodextrins has been carried out in order to determine the apparent stability constants of the complexes and the thermodynamic parameters associated to complexation.     

Molecular dynamics simulations of the mononuclear zinc-beta-lactamase from Bacillus cereus complexed with benzylpenicillin and a quantum chemical study of the reaction mechanism

Herein, we present results from MD simulations of the Michaelis complex formed between the B. cereus zinc-beta-lactamase enzyme and benzylpenicillin. The structural and dynamical effects induced by substrate-binding, the specific role of the conserved residues, and the near attack conformers of the Michaelis complex are discussed. Quantum chemical methods (HF/6-31G* and B3LYP/6-31G*) are also applied to study the hydrolysis reaction of N-methylazetidinone catalyzed by a monozinc system consisting of the side chains of the histidine residues (His86, His88, and His149) complexed with Zn-OH and the side chains of Asp90 and His210. From this model system, we built molecular-mechanics representations of the prereactive complex and transition state configurations docked into the active site. Linear-scaling semiempirical calculations coupled with a continuum solvent model were then performed on these static models. We propose that the experimental rate data for the B. cereus enzyme is compatible with a one-step mechanism for the hydrolysis of beta-lactam substrates in which His210 acts as a proton donor.     

Enzyme catalysis in organic solvents: a promising field for optical biosensing

The ability of enzymes to work in non-aqueous media offers new and almost unexploited possibilities for the development of new optical biosensors. The advantages of performing biocatalytic reactions in non-aqueous media are discussed in relation to their possible application in optical biosensor design. Attention is focused on the factors that influence enzymatic catalysis in organic solvents, including the role of enzyme-associated water, criteria for solvent selection and the alteration of enzyme specificity. Recent examples of relevant applications and future prospects of organic-phase optical biosensing are discussed.     

Extraction of the (C4H9)4N+Co(II)SCN− ion-pair in chloroform and in isoamyl alcohol: Spectrophotometric determination of cobalt

When excesses of ammonium thiocyanate and tetrabutylammonium chloride are added to a cobalt(II) solution, a water-insoluble ion-pair is formed; this compound is soluble in chloroform, isoamyl alcohol, and other solvents. The variables which affect the extractions by these two solvents are studied in order to obtain the optimal conditions and two alternative extraction procedures are proposed. Thus, the separation of cobalt as a previous step for its spectrophotometric determination is studied.     

The crystal structure of eudesma-4(15),7(11)-dien-8α, 12-olide: a sesquiterpene lactone fromTrattinickia rhoifolia Willd

The title compound, formula C₁₅H₂₀O₂, is orthorhombic, P2₁2₁2₁ witha=8.747(2),b=12.025(3),c=12.554(3)Å,Z=4, andD _m =1.32(2)g/ml. The structural analysis shows that the compound corresponds to eudesma-4(15),7(11)-dien-8,12-olide, a sesquiterpene lactone previously isolated fromAster umbellatus but whose crystal structure was unknown.     

Individual extraction constants of some dicarbollylcobaltate anions in the water-nitrobenzene system

Individual extraction constants of nine dicarbollylcobaltate anions in the two-phase water-nitrobenzene system were determined radiometrically assuming that the changes of Gibbs energy of the transfer of the tetraphenylarsonium cation, Ph₄As⁺, and of the tetraphenylborate anion, BPh ₄ ^– , from the aqueous into the nitrobenzene phase are equal. The constants obtained by this method were correlated with Hansch's constants of hydrophobity.