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.     

On the continuation for variational inequalities depending on an eigenvalue parameter

In this paper we generalize recent theoretical results on the local continuation of parameter-dependent non-linear variational inequalities. The variational inequalities are rather general and describe, for example, the buckling of beams, plates or shells subject to obstacles. Under a technical hypothesis that is satisfied by the simply supported beam, we obtain the existence of a continuation of both the solution and the eigenvalue with respect to a local parameter. A numerical continuation method is presented that easily overcomes turning points. Numerical results are presented for the non-linear beam.     

Negative luminescence from mid-wave infrared HgCdTe diode arrays

A self-referencing, optical modulation technique was used to measure the negative luminescence efficiencies of an array of mid-wave infrared HgCdTe photodiodes with cutoff wavelength 4.6 μm as a function of sample temperature. The internal efficiency at a wavelength of 4 μm was 93% at 295 K, and nearly independent of temperature in the 240–300 K range. This corresponds to an apparent temperature reduction >50 K at room temperature and >30 K at 240 K. Moreover, the reverse-bias saturation current density was only 0.13 A/cm². The measured transmission and emission spectra were simulated using empirical HgCdTe absorption formulas from the literature.     

Model for describing the production of Centauro events and strangelets in heavy-ion collisions

A phenomenological model for describing the production of Centauro events in relativistic heavy-ion collisions is discussed. The model provides quantitative predictions for kinematical variables, for the baryon number, and for the masses of a Centauro fireball and of its decay products. A Centauro fireball decays predominantly into nucleons, strange hyperons, and possibly strangelets. Centauro events in Pb + Pb collisions at the LHC energy are simulated for the CASTOR detector. The signatures of these events are discussed in detail.     

Atom transfer radical polymerization of methyl methacrylate by copper(I)‐pyridine‐2‐carboximidate catalysts

Pyridine‐2‐carboximidates [methyl ( 1a ), ethyl ( 1b ), isopropyl ( 1c ), cyclopentyl ( 1d ), cyclohexyl ( 1e ), n‐octyl ( 1f ), and benzyl ( 1g )] were prepared from the reaction of 2‐cyanopyridine with the corresponding alcohols. Cyclopentyl‐substituted 1d was found to be a highly effective ligand for copper‐catalyzed atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). For example, the observed rate constant for a CuBr/ 1d catalytic system was found to be nearly twice as high as the cyclohexyl‐substituted CuBr/ 1e catalytic system [k_obs = (1.19 vs 0.56) × 10^?4 s^?1). The effects of the solvents, temperature, catalyst/initiator, and solvent/monomer ratio on the ATRP of MMA were studied systematically for the CuBr/ 1d catalytic system. The optimum condition for the ATRP of MMA was found to be a 1:2:1:400 [CuBr]_o/[ 1d ]_o/[ethyl 2‐bromoisobutyrate]_o/[MMA]_o ratio at 60 °C in veratrole solution, which yielded well‐defined poly(MMA) with a narrow molecular weight distribution of 1.14. The catalytically active copper complex 2d was isolated from the reaction of CuBr with 1d . Narrow molecular weight distributions as low as 1.06 were achieved for the CuBr/ 1d catalytic system by employing 10% of the deactivator CuBr₂. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2747–2755, 2004     

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