Preparation of rhodium–phyllosilicate catalysts without leaching in liquid-phase 1-hexene hydrogenation

Rhodium catalysts have been prepared on palygorskite and montmorillonite (clay) supports by reduction with hydrogen (1 atmosphere) at room temperature of a cationic organometallic rhodium compound anchored to the support. The activity of these catalysts for the hydrogenation of liquid-phase 1-hexene remains constant with increase of prehydrogenation time and with re-use for several runs. No rhodium leaching is observed.     

The interaction between poly(N-isopropylacrylamide) and salts in aqueous media: The “salting-out” phenomenon as studied by attenuated total reflection/fourier transform infrared spectroscopy

The effect of two strong salting-out salts (Na₂SO₄ and K₂SO₄) on the temperature-induced phase-separation process in aqueous solutions of poly(N-isopropylacrylamide) (PNIPA) was examined by attenuated total reflectance/Fourier transform infrared spectroscopy, differential scanning calorimetry, and viscosity measurements. On the basis of these measurements, a detailed scenario of the phase-separation process was deduced. The phase-separation scenario of solutions containing PNIPA and water was altered in the presence of sulfate ions. Here, the sulfate ions induced partial intrachain collapse, manifested by a relatively compact structure well below the lower critical solution temperature. This led to a more gradual, smooth phase transition, with temperature-resolved intrachain collapse and interchain aggregation and a lesser extent of hysteresis. Although at the macrolevel one may not be able to differentiate among various scenarios altering the solvent into a poor solvent, the aforementioned microlevel measurements provided a way to expose the difference between raising the temperature and adding cosolutes. Follow-up studies on the effect of salting-in salts will be presented. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 33–46, 2004     

Analysing the effect of technical change on individual outputs using modified quasi-Malmquist indexes

Malmquist indexes can be used to estimate technical change over time. The index generally represents the average effect of technical change on all outputs in a multi-output firm. However, changes in technology do not necessarily affect all outputs involved in the analysis equally. In this paper, a method for estimating the effect of technical change on each of the different outputs is proposed. This estimation is done by a modification of quasi-Malmquist indexes. An artificial data set has been used to validate the method proposed in this paper.     

Sustainability in bankruptcy problems

This paper focuses on a new property for bankruptcy rules, calledsustainability, which requires that the agents with small enough claims be fully reimbursed. We show that the constrained equal-awards rule is the only rule that satisfies path independence and sustainability. Exploiting duality relations, we also provide a characterization of the constrained equal-losses rule, as the only one that satisfies composition and independence of residual claims (the dual property of sustainability).     

A parametric study of surface-discharge nitrogen lasers

A parametric study of sandwich-type discharge chamber nitrogen lasers has been carried out. A non-monotonic dependence of the energy emitted by the laser and the discharge chamber thickness is found. Discharge chambers with = 1 have the best electro-optical efficiency. The ratio between the electrode gap,d, and is found to be a scaling parameter. The possible influence of wall ablation in the comportment is also discussed.     

Determination of six metals in galician red wines (in northwestern Spain) by capillary electrophoresis

A simple technique is described for the routine simultaneous capillary electrophoretic determination of 6 cations in wine. Separation was achieved on a fused silica capillary column with a UV-Cat-1, alpha-hydroxysobutyric acid and 18-crown-6-ether buffer at pH 4.5 and indirect UV detection at 214 nm. The content of magnesium, sodium, potassium, calcium, manganese, and lithium was determined. The method is quantitative, with recoveries in the 92-102% range, and linear over more than one order of magnitude. The precision is better than 2.5-3.4%. The method is sensible, with detection limits between 0.01 and 0.06 mg/L. Twenty-five red wines with a Certified Brand of Origin from Galicia (north-western Spain) were analyzed by the proposed method. Various wines showed very similar electrophoretic profiles, but significant quantitative differences were observed.     

Influence of rotation and isotope effects on the dynamics of the N((2)D)+H(2) reactive system and of its deuterated variants

Integral cross sections and thermal rate constants have been calculated for the N((2)D)+H(2) reaction and its isotopic variants N((2)D)+D(2) and the two-channel N((2)D)+HD by means of quasiclassical trajectory and statistical quantum-mechanical model methods on the latest ab initio potential-energy surface [T.-S. Ho et al., J. Chem. Phys. 119, 3063 (2003)]. The effect of rotational excitation of the diatom on the dynamics of these reactions has been investigated and interesting discrepancies between the classical and statistical model calculations have been found. Whereas a net effect of reagent rotation on reactivity is always observed in the classical calculations, only a very slight effect is observed in the case of the asymmetric N((2)D)+HD reaction for the statistical quantum-mechanical method. The thermal rate constants calculated on this Potential-Energy Surface using quasiclassical trajectory and statistical model methods are in good agreement with the experimental determinations, although the latter are somewhat larger. A reevaluation of the collinear barrier of the potential surface used in the present study seems timely. Further theoretical and experimental studies are needed for a full understanding of the dynamics of the title reaction.     

Multiresidue determination of fluoroquinolones in shrimp by liquid chromatography-fluorescence-mass spectrometry

An efficient multiresidue method for analysis of fluoroquinolones in shrimp has been developed in which quantitation by fluorescence and confirmation by Multiple Stage Mass Spectrometry (MS) is achieved simultaneously. In this method, shrimp tissue is extracted with ammoniacal acetonitrile and the extract is defatted and then evaporated. After dissolution in basic phosphate buffer, fluoroquinolones in the extract are separated by liquid chromatography and quantitated, taking advantage of their intense fluorescence. Eluate from the fluorescence detector enters the MS, which allows for confirmation by monitoring ratios of 2 prominent product ions in the MS3 or MS2 spectrum. Using this method, 8 fluoroquinolones have been analyzed in shrimp samples fortified at 10, 25, 50, or 100 ppb levels. Recoveries for desethyleneciprofloxacin, norfloxacin, ciprofloxacin, danofloxacin, enrofloxacin, orbifloxacin, sarafloxacin, and difloxacin ranged from 75 to 92%, with relative standard deviation values of <6%. The limits of quantitation ranged from 0.1 to 1 ng/g. Enrofloxacin and ciprofloxacin were also successfully determined in enrofloxacin-incurred shrimp using this method.     

Effect of ionic strength on the formal potential of the glass electrode in various saline media

We examined the variation with ionic strength (I, adjusted with KCl, KNO₃, KBr, NaCl or NaClO₄) of the formal potential (E_const) for glass electrodes exhibiting a Nernstian response (i.e. E_cell=E_const−s log [H⁺]). For this purpose, we investigated the different factors included in the formal potential, so we obtained reported values for the liquid junction potential as a function of ionic strength and determined the logarithm of the activity coefficient for the proton in various saline media, using Pitzer equations.