Partition coefficients of environmentally important phenols in a supercritical carbon dioxide-water system from cocurrent extraction without analysis of the compressible phase

Partition coefficients of phenol, salicylic acid, and several environmentally important chloro- and nitrophenols in a supercritical CO2-water system were measured using direct cocurrent extraction of aqueous solutions of the individual solutes with CO2. Partitioning data on the nitrophenols and salicylic acid were obtained for the first time. To bypass the troublesome and error-prone analysis of the CO2-rich phase, the present method employed only the solute concentrations in the aqueous phase before and after extraction to determine the partition coefficient. Unlike most previous engineering studies of phenol partitioning in a CO2-water system, the concentrations of phenolic solutes approached infinite dilution in both phases. This makes the results relevant to analytical-scale SFE of environmental water samples with CO2. Because of effective infinite dilution of the solutes, the partition coefficients provide a direct measure of relative CO2-philicity/hydrophilicity of the individual phenols. Compared to the octanol-water partition coefficients of substituted phenols, the CO2-water partition coefficients are more sensitive to substitution in the position neighboring the hydroxyl group.     

A new wavelet-based measure of image focus

We present a new measure of image focus. It is based on wavelet transform of the image and is defined as a ratio of high-pass band and low-pass band norms. We show this measure is monotonic with respect to the degree of defocusation and sufficiently robust. We experimentally illustrate its performance on simulated as well as real data and compare it with existing focus measures (gray-level variance and energy of Laplacian). Finally, an application of the new measure in astronomical imaging is shown.     

Analysis of the reaction mechanism and substrate specificity of haloalkane dehalogenases by sequential and structural comparisons

Haloalkane dehalogenases catalyse environmentally importantdehalogenation reactions. These microbial enzymes representobjects of interest for protein engineering studies, attemptingto improve their catalytic efficiency or broaden their substratespecificity towards environmental pollutants. This paper presentsthe results of a comparative study of haloalkane dehalogenasesoriginating from different organisms. Protein sequences andthe models of tertiary structures of haloalkane dehalogenaseswere compared to investigate the protein fold, reaction mechanismand substrate specificity of these enzymes. Haloalkane dehalogenasescontain the structural motifs of /ß-hydrolases and epoxidaseswithin their sequences. They contain a catalytic triad withtwo different topological arrangements. The presence of a structurallyconserved oxyanion hole suggests the two-step reaction mechanismpreviously described for haloalkane dehalogenase from Xanthobacterautotrophicus GJ10. The differences in substrate specificityof haloalkane dehalogenases originating from different speciesmight be related to the size and geometry of an active siteand its entrance and the efficiency of the transition stateand halide ion stabilization by active site residues. Structurallyconserved motifs identified within the sequences can be usedfor the design of specific primers for the experimental screeningof haloalkane dehalogenases. Those amino acids which were predictedto be functionally important represent possible targets forfuture site-directed mutagenesis experiments.     

Reactant partitioning in free-radical heterophase polymerization: The case of inverse microemulsion polymerization of acrylamide

Conversion curves have been determined at 60°C for the polymerization of acrylamide in percolating inverse microemulsions. Ammonium peroxo-disulphate (APS) and dibenzoyl peroxide (DBP) were used as initiators of free-radical polymerization in the presence or absence of potassium nitrosodisulphonate (Fremy's salt, FS). The percolation decreases the rate of polymerization of acrylamide initiated by APS. The polymerization is inhibited by FS. After an inhibition period, retardation of acrylamide polymerization is more pronounced in non-percolating microemulsions. No inhibition periods were observed for DBP-initiated polymerization of acrylamide. The percolation shortens the time interval of the ‘slow’ polymerization of acrylamide, but the rates of rapid acrylamide polymerization above 10% conversion are the same for percolating and for non-percolating inverse microemulsions. The polymer particle diameter is a function of acrylamide/water weight ratio and of [water]/[AOT] (AOT: bis(2-ethylhexyl)-sulphosuccinate sodium salt) molar ratio. No effect of the initiator's nature either in the presence or in the absence of FS was found. The results are interpreted on the basis of initiator and/or nitroxide radical partitioning between oil and water phases of the inverse microemulsion, and are discussed with respect to the mechanism of acrylamide polymerization and polymer particle formation proposed for non-percolating inverse microemulsions.     

Poly(methyl methacrylate) and polyacrylonitrile dispersions stabilized by gelatin

Methyl methacrylate was polymerized in an aqueous medium in the presence of gelatin using potassium persulfate as initiator. The dispersion mode of polymerization, when the monomer is completely miscible with water, was investigated and compared with an emulsion process, which proceeds at higher monomer concentration. Spherical and relatively uniform polymer particles were formed. Macroscopic precipitation of polymer is prevented by combination of the steric stabilization by grafted gelatin and of repulsive electrostatic interactions from the initiator residues attached to the particle surface. Static and dynamic light scattering have been used to determine the molar mass (molar mass of the whole dispersion particle, M_wD ～ 10⁸-10⁹ g mol^?1) and hydrodynamic radius (R_hD ～ 50-120 nm) of the particles. The number of particles per unit volume does not depend on overall monomer concentration, and it is higher, and therefore the particle size is smaller, than that observed for the soapless emulsion polymerization. The addition of gelatin may be thus used to modify the particle size. Acrylonitrile dispersions were prepared under similar conditions. Unlike methyl methacrylate, this monomer does not swell the polymer particles. While poly(methyl methacrylate) particles are spherical and relatively uniform, the polyacrylonitrile dispersions consist of polydisperse aggregates of tiny polymer particles.     

Influence of oxygen partial pressure and substrate temperature during vapour deposition on the structural properties of CdSe films

CdSe films prepared in vacuum by sublimation from the compound at oxygen partial pressures in the residual atmosphere from 2.8 × 10^?5 to 3.2 × 10^?4 Torr and at substrate temperatures of 295 and 523 K were subjected to X-ray structural analysis. The results obtained are analysed and discussed in terms of some structures different from those of CdSe, e.g. CdSeO₃ and CdSeO₃.SeO₂.     

Aldehyde functionalization of styrene polymers

Summary Two methods of the introduction of aldehyde group into polystyrene skeleton are described.     

Toxicity increases in ice containing monochlorophenols upon photolysis: environmental consequences

The toxic effects of photoproducts formed upon the photolysis of 2- and 4-chlorophenol (CP) frozen solutions in polycrystalline ice phase were determined with a bacterial luminescence test (Vibrio fisheri), and in vitro biomarker assay for dioxin-like effects (inductions of AhR-dependent luciferase in H4IIE-luc cells) and compared to the toxic effects of products of the same photoreaction in aquatic phase. Coupling photoproducts formed in ice samples (3'-chlorobiphenyl-2,4'-diol and 3-chlorobiphenyl-2,2'-diol from 2-CP photolysis and 5-chlorobiphenyl-2,4'-diol from 4-CP photolysis) were found to be more toxic to V. fisheri than parent CPs and elicited significant inductions of dioxin-like effects (the effective concentrations EC50 approximately 3 x 10(-5) mol L(-1) corresponded to known weaker ligands of AhR, such as nonplanar polychlorinated biphenyls or polycyclic aromatic hydrocarbons). To complete the picture, a photoproduct formed from 4-CP (5-chlorobiphenyl-2,4'-diol) was synthesized, and a detailed toxicity assessment with purified compound confirmed the results obtained with irradiated samples. Our findings support a recently proposed model according to which solar radiation can trigger the formation of new types of organic pollutants in polar ice or tropospheric ice cloud particles, presenting possibly greater risk to the environment than the parent compounds.     

Czech results at criticality dosimetry intercomparison 2002

Two criticality dosimetry systems were tested by Czech participants during the intercomparison held in Valduc, France, June 2002. The first consisted of the thermoluminescent detectors (TLDs) (Al-P glasses) and Si-diodes as passive neutron dosemeters. Second, it was studied to what extent the individual dosemeters used in the Czech routine personal dosimetry service can give a reliable estimation of criticality accident exposure. It was found that the first system furnishes quite reliable estimation of accidental doses. For routine individual dosimetry system, no important problems were encountered in the case of photon dosemeters (TLDs, film badge). For etched track detectors in contact with the 232Th or 235U-Al alloy, the track density saturation for the spark counting method limits the upper dose at approximately 1 Gy for neutrons with the energy >1 MeV.     

Static load balancing applied to Schur complement method

A finite element method often leads to large sparse symmetric and positive definite systems of linear equations. We consider parallel solvers based on the Schur complement method on homogeneous parallel machines with distributed memory. A finite element mesh is partitioned by graph partitioning. Such partitioning results in submeshes with similar numbers of elements and, consequently, submatrices of similar sizes. The submatrices are partially factorised. The time spent on the partial factorisation can be different, i.e., disbalanced, because methods exploiting the sparsity of submatrices are used. This paper proposes a Quality Balancing heuristic that modifies classic mesh partitioning so that the partial factorisation times are balanced, which saves overall computation time, especially for time dependent mechanical and nonstationary transport problems.