Solid-phase microextraction–capillary gas chromatography combined with microwave-induced plasma atomic-emission spectrometry for selenite determination

The use of solid-phase microextraction (SPME) with gas chromatography coupled to microwave-induced plasma atomic-emission detection (GC–MIP-AED) is described for selenite [Se(IV)] speciation. Aqueous standards were derivatised with sodium tetraethyl- or tetrapropylborate and extracted by SPME. Headspace extraction of the ethyl and propyl derivatives was studied. Relevant experimental conditions were optimised, including conditions for derivatisation and extraction and those of gas chromatographic analysis. The limits of detection achieved for headspace sampling of derivatised Se(IV) were in the low ng mL^–1 range for both ethylation and propylation. When the method was applied to analysis of selenite in selenised yeast reference material results were in good agreement with the indicated values.     

The Effect of Cyclodextrins on the Photochemical Stability of 7-Amino-4-methylcoumarin in Aqueous Solution

The effect of -, - and -cyclodextrin onthe photochemical stability of 7-amino-4-methylcoumarin (C120)was studied. Using spectroscopic techniques (UV/Vis absorption spectroscopy, fluorescence, fluorescence anisotropy and circular dichroism) combined with HPLC/MS and MS analysis it was demonstrated that addition of -cyclodextrin to the aqueoussolution of C120 markedly inhibits the photodegradation of that dye. This results from theformation of an inclusion complex between C120 and -cyclodextrin.     

Pretreatment of sugarcane bagasse hemicellulose hydrolysate for xylitol production byCandida guilliermondii

Applied Biochemistry and Biotechnology - In order to remove or reduce the concentrations of toxic substances present in the sugarcane bagasse hemicellulose hydrolysate for xyloseto-xylitol...     

Determination of fluquinconazole, pyrimethanil, and clofentezine residues in fruits by liquid chromatography with ultraviolet detection

A simple method was developed for the determination of fluquinconazole, pyrimethanil, and clofentezine in whole fruit; peel; and pulp of mango, apple, and papaya. These compounds were extracted from fruit samples with a mixture of ethyl acetate-n-hexane (1 + 1, v/v). An aliquot (2 mL) of the extract was evaporated to near dryness under a stream of nitrogen, and the residue was dissolved with 2 mL methanol. The analysis was performed by means of liquid chromatography with ultraviolet detection at 254 nm using a gradient solvent system. The method was validated with fortified fruit samples at concentration levels of 0.05, 0.10, 0.20, and 0.50 mg/kg. Average recoveries (4-8 replicates) ranged from 80 to 95% with relative standard deviations between 3.5 and 12.7%. Detection limits ranged from 0.03 to 0.05 mg/kg for fruit pulp and 0.03 mg/kg for whole fruit. The quantitation limits ranged from 0.05 to 0.10 mg/kg for fruit pulp and 0.05 mg/kg for whole fruit. The analytical method was applied to fruit samples obtained from local markets.     

Two-plane sub-bundles of nonorientable real vector-bundles

Let be a nonorientable m-plane bundle over a CW complex X of dimension m or less. Given a 2-plane bundle over X, we wish to know whether can be embedded as a sub-bundle of . The bundle need not be orientable. When is even-dimensional there is the added complication of twisted coefficients. In that case, we use Postnikov decomposition of certain nonsimple fibrations in order to describe the obstructions for the embedding problem. Emery Thomas [11] and [12] treated this problem for and both orientable. The results found here are applied to the tangent bundle of a closed, connected, nonorientable smooth manifold, as a special case.The writing of this paper was partially supported by CNPq grant     

On finite {1,2,3}-semiaffine planes

In this paper, we investigate {1,2,3}-semiaffine planes. All such planes of order n >51 shall be classified. It turns out that they are embeddable into projective planes of the same order n in the most natural way.Work supported by National Research Project on Strutture Geometriche Combinatoria, loro applicazioni of Italian M.P.I. and G.N.S.A.G.A. of C.N.R.     

Hydrodynamic equations for attractive particle systems on ℤ

Hydrodynamic properties for a class of nondiffusive particle systems are investigated. The method allows one to study local equilibria for a class of asymmetric zero-range processes, and applies as well to other models, such as asymmetric simple exclusion and misanthropes. Attractiveness is an essential ingredient. The hydrodynamic equations present shock wave phenomena. Preservation of local equilibrium is proven to hold away from the shocks. The problem of breakdown of local ergodicity at the shocks, which was investigated by D. Wick in a particular model, remains open in this more general setup.     

Intra- and intermolecular fluorescence quenching in 7-(pyridyl)indoles

Three isomeric 7-(pyridyl)indoles reveal very different, solvent-dependent photophysical properties. Due to rapid excited state depopulation involving intramolecular hydrogen bonding, 7-(2′-pyridyl)indole is practically nonfluorescent at room temperature. In nonpolar and polar aprotic solvents, 7-(3′-pyridyl)indole and 7-(4′-pyridyl)indole fluorescence strongly, but the emission is quenched in alcohols. Syn and anti rotameric forms of 7-(3′-pyridyl)indole are detected, each quenched to a different degree. This differential quenching is interpreted as evidence of enhanced S₁ → S₀ internal conversion being more efficient in cyclic solvates, with alcohol molecules forming a bridge between the proton donor and acceptor groups of an excited chromophore.     

Parameterization of peptide 13C carbonyl chemical shielding anisotropy in molecular dynamics simulations.

NMR chemical shielding anisotropy (CSA) relaxation is an important tool in the study of dynamical processes in proteins and nucleic acids in solution. Herein, we investigate how dynamical variations in local geometry affect the chemical shielding anisotropy relaxation of the carbonyl carbon nucleus, using the following protocol: 1) Using density functional theory, the carbonyl (13)C' CSA is computed for 103 conformations of the model peptide group N-methylacetamide (NMA). 2) The variations in computed (13)C' CSA parameters are fitted against quadratic hypersurfaces containing cross terms between the variables. 3) The predictive quality of the CSA hypersurfaces is validated by comparing the predicted and de novo calculated (13)C' CSAs for 20 molecular dynamics snapshots. 4) The CSA fluctuations and their autocorrelation and cross correlation functions due to bond-length and bond-angle distortions are predicted for a chemistry Harvard molecular mechanics (CHARMM) molecular dynamics trajectory of Ca(2+)-saturated calmodulin and GB3 from the hypersurfaces, as well as for a molecular dynamics (MD) simulation of an NMA trimer using a quantum mechanically correct forcefield. We find that the fluctuations can be represented by a 0.93 scaling factor of the CSA tensor for both R(1) and R(2) relaxations for residues in helix, coil, and sheet alike. This result is important, as it establishes that (13)C' relaxation is a valid tool for measurement of interesting dynamical events in proteins.     

Multistep energy transfer in single molecular photonic wires

We demonstrate the synthesis and spectroscopic characterization of an unidirectional photonic wire based on four highly efficient fluorescence energy-transfer steps (FRET) between five spectrally different chromophores covalently attached to double-stranded DNA. The DNA-based modular conception enables the introduction of various chromophores at well-defined positions and arbitrary interchromophore distances. While ensemble fluorescence measurements show overall FRET efficiencies between 15 and 30%, single-molecule spectroscopy performed on four spectrally separated detectors easily uncovers subpopulations that exhibit overall FRET efficiencies of up to approximately 90% across a distance of 13.6 nm and a spectral range of approximately 200 nm. Fluorescence trajectories of individual photonic wires show five different fluorescence intensity patterns which can be ascribed to successive photobleaching events.