Combined supercritical-fluid chromatography/mass spectrometry in the analysis of diuron in plasma using on-line phase-system switching

On-line sample pretreatment by means of the phase-system switching approach is an interesting technique for the analysis of aqueous samples, e.g., plasma, by means of supercritical-fluid chromatography. In order to analyse plasma samples the following analytical procedure is used. The plasma sample is injected on to a short precolumn, which is washed with water and subsequently dried with nitrogen. Next, the solutes are desorbed with the supercritical mobile phase, analysed with packed-column supercritical-fluid chromatography and detected with either a UV detector or a mass spectrometer, equipped with a moving-belt interface. The herbicide diuron is selected as a test compound to study the feasibility of this approach. Using a selective detector the procedure is sufficiently sensitive to detect diuron in plasma, but not appropriate to detect the diuron metabolites in a post-mortem plasma sample. These have been identified with liquid chromatography/mass spectrometry. The detection limit of diuron in plasma using the procedure described is about 30 ng/mL.     

Characterization of thermal diffusion in polymer solutions by thermal field-flow fractionation: Dependence on polymer and solvent parameters

The thermal diffusion coefficient D_T has been obtained for 17 polymer-solvent combinations, each of them spanning a range of polymer molecular weights, using thermal field-flow fractionation. The polymers examined include polystyrene, poly(alpha-methyl)styrene, polymethylmethacrylate, and polysioprene. The solvents include benzene, toluene, ethylbenzene, tetrahydrofuran, methylethylketone, ethylacetate, and cyclohexane. Although D_T was confirmed as essentially independent of polymer molecular weight, it was found to vary substantially with the chemical composition of polymer and solvent. The results were used to evaluate several thermal diffusion theories; the agreement with theory was generally found to be unsatisfactory. Attempts were then made to correlate the measured thermal diffusion coefficients with various physicochemical parameters of the polymers and solvent. A good correlation was found in which D_T increases with the thermal conductivity difference of the polymer and solvent and varies inversely with the activation energy of viscous flow of the solvent.     

Yellow‐light‐emitting cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative: Its synthesis and optical properties

A soluble cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative ( 9 ) was synthesized and characterized. Comparison between 9 and its model compound ( 10 ) showed that the chromophore in 9 remained to be well defined as a result of a π‐conjugation interruption at adjacent m‐phenylene units. The attachment of a cyano substituent only at the β position of the vinylene allowed the maximum electronic impact of the cyano group on the optical properties of the poly(p‐phenylene vinylene) material. At a low temperature (?108 or ?198 °C), the vibronic structures of 9 and 10 were partially resolved. The absorption and emission spectra of a film of 9 were less temperature‐dependent than those of a film of 10 , indicating that the former had a lower tendency to aggregate. A light‐emitting diode (LED) based on 9 emitted yellow light (λ_max ≈ 578 nm) with an external quantum efficiency of 0.03%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3149–3158, 2003     

Roles of rhenium diimine complexes as metal‐ion probes and photosensitizers in functional polyurethanes

Polyurethanes incorporated with rhenium diimine complexes were synthesized. The polymers exhibited interesting morphologies and solution properties. Results from gel permeation chromatography suggested the formation of polymer aggregates in solutions. The polymers could act as probes for metal ions. The addition of metal ions to polymer solutions led to significant changes in the electronic absorption properties of the polymer solutions. This was attributed to the interactions between the polyether moieties and metal ions. The metal complexes could also act as efficient photosensitizers. After doping with charge‐transport viologens, the photoconductivity of the polymers was greatly enhanced. The experimental quantum efficiency was simulated with Onsager's theory. The thermalization distances and the primary yields were typically 12–14 Å and 10^?3, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1708–1715, 2003     

A transform method for linear evolution PDEs on a finite interval

We study initial boundary value problems for linear scalar evolutionpartial differential equations, with spatial derivatives ofarbitrary order, posed on the domain {t > 0, 0 < x <L}. We show that the solution can be expressed as an integralin the complex k-plane. This integral is defined in terms ofan x-transform of the initial condition and a t-transform ofthe boundary conditions. The derivation of this integral representationrelies on the analysis of the global relation, which is an algebraicrelation defined in the complex k-plane coupling all boundaryvalues of the solution. For particular cases, such as the case of periodic boundaryconditions, or the case of boundary value problems for even-orderPDEs, it is possible to obtain directly from the global relationan alternative representation for the solution, in the formof an infinite series. We stress, however, that there existinitial boundary value problems for which the only representationis an integral which cannot be written as an infinite series.An example of such a problem is provided by the linearized versionof the KdV equation. Similarly, in general the solution of odd-orderlinear initial boundary value problems on a finite intervalcannot be expressed in terms of an infinite series.     

Banana-shaped mesogens: a new homologous series of compounds exhibiting the B7 mesophase

The synthesis and characterization of a new homologous series of compounds, the 2-cyano-1,3-phenylene bis[4-(4-n-alkoxyphenyliminomethyl)benzoates] derived from 2-cyanoresorcinol is reported. All the compounds are enantiotropic mesogens and exhibit the fascinating B₇ mesophase. The characterization of the mesophase was performed using polarizing optical microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical studies.     

Fractional Derivatives Applied to Phase-Space Reconstructions

The concept and application of phase-space reconstructions are reviewed. Fractional derivatives are then proposed for the purpose of reconstructing dynamics from a single observed time history. A procedure is presented in which the fractional derivatives of time series data are obtained in the frequency domain. The method is applied to the Lorenz system. The ability of the method to unfold the data is assessed by the method of global false nearest neighbors. The reconstructed data is used to compute recurrences and correlation dimensions. The reconstruction is compared to the commonly used method of delays in order to assess the choice of reconstruction parameters, and also the quality of results.