Zero-temperature equation of state of quasi-one-dimensional H2

We have studied molecular hydrogen in a pure 1D geometry and inside a narrow carbon nanotube by means of the diffusion Monte Carlo method. The one dimensionality of H2 in the nanotube is well maintained in a large density range, this system being closer to an ideal 1D fluid than liquid 4He in the same setup. H2 shares with 4He the existence of a stable liquid phase and a quasicontinuous liquid-solid transition at very high linear densities.     

Strong correlation effects in 2D Bose-Einstein condensed dipolar excitons

By doing quantum Monte Carlo ab initio simulations we show that dipolar excitons, which are now under experimental study, actually are strongly correlated systems. Strong correlations manifest in significant deviations of excitation spectra from the Bogoliubov one, large Bose condensate depletion, short-range order in the pair correlation function, and peak(s) in the structure factor.     

Stability of the intersection of solution sets of semi-infinite systems

Many mathematical programming models arising in practice present a block structure in their constraint systems. Consequently, the feasibility of these problems depends on whether the intersection of the solution sets of each of those blocks is empty or not. The existence theorems allow to decide when the intersection of non-empty sets in the Euclidean space, which are the solution sets of systems of (possibly infinite) inequalities, is empty or not. In those situations where the data (i.e., the constraints) can be affected by some kind of perturbations, the problem consists of determining whether the relative position of the sets is preserved by sufficiently small perturbations or not. This paper focuses on the stability of the non-empty (empty) intersection of the solutions of some given systems, which can be seen as the images of set-valued mappings. We give sufficient conditions for the stability, and necessary ones as well; in particular we consider (semi-infinite) convex systems and also linear systems. In this last case we discuss the distance to ill-posedness.     

New cycloaddition reactions of 1-phenyl-4-vinylpyrazole

1-Phenyl-4-vinylpyrazole reacts with methyl propiolate and N-phenylmaleimide giving via the Diels-Alder 1:1 adducts, products (4) and (8), and also the 1:2 adducts (5), (6) and (9) resulting from an “ene” reaction of the initially forced cycloadducts. The obtention of the adducts (5) and (6) in equimolecular amounts is a good example of the non-regioselective character of the “ene” reaction. The reaction with tetracyanoethylene takes place through the olefinic substituent giving the π² + π² adduct (10).     

Rapid flow injection method for the determination of sulfite in wine using the permanganate-luminol luminescence system

A simple, rapid and sensitive chemiluminescence method for the determination of sulfite has been developed by combining flow-injection analysis and its sensitizing effect on the known chemiluminescence emission produced by the oxidation of luminol in alkaline medium; in this work permanganate has been proposed as oxidizing reactive. The optimum conditions for the chemiluminescence emission were established. The chemiluminescence was proportional to the sulfite concentration over the range 1.6 × 10⁻⁵ and 4.0 × 10⁻⁴ mol L⁻¹. The detection limit was 4.7 × 10⁻⁶ mol L⁻¹ of sulfite. The method has been satisfactorily used for the determination of free and bound sulfite in wines.     

Influence of Rubber Formulation on Surface Modifications Produced by RF Plasma

The effectiveness of nitrogen, oxygen and air Radio Frequency (RF) plasma treatments on two styrene-butadiene vulcanized rubbers with a different formulation has been studied. The presence of an antiadherent surface layer containing low-molecular weight ingredients (sulfur-rich vulcanization agents and wax) from SW (Sulfur-Wax) rubber formulation requires an extended plasma treatment capable of removing this surface layer. When the percentage of antiadherent moieties is reduced in ZS (Zinc Stearate) rubber formulation, shorter plasma treatment times are enough to modify rubber surface and increase its polarity by the creation of C–O and C=O polar groups that enhance adhesion towards a polyurethane adhesive. Air and oxygen plasma treatments are more aggressive than nitrogen plasma and therefore they are more effective in removing the antiadherent layer of the outermost rubber surface layer prior to oxidation of the rubber surface.     

Continuous solid-phase extraction method for the determination of amines in human urine following on-line microwave-assisted acid hydrolysis

Humans are exposed to endogenous or exogenous formation of aromatic amines (AAs) and N-nitrosamines (NAms), which are considered to be potent carcinogens. The objective of this study was to monitor AAs and NAms in human urine to obtain a way to assess exposure. However, while NAms can be directly detected in urine samples, AAs require hydrolysis to convert their conjugates into free amines. A semiautomatic flow-base method is proposed for the simultaneous determination of aliphatic and aromatic NAms, anilines and chloroanilines in human urine in one analytical run. Conjugated AAs are released from urine by on-line microwave-assisted acid hydrolysis without degradation of NAms; all amines were then preconcentrated using solid-phase extraction. Separation/determinations are carried out by gas chromatography and mass spectrometry operating in selected ion monitoring mode. The method is fast (∼15 min for 25 mL of sample) and provides low limits of detection (from 2 to 26 ng/L) with good precision (relative standard deviation within and between days less than 7%). Finally, the proposed method was successfully applied to check AAs and NAms in the human urine of exposed and unexposed researchers. The kinetics of amine excretion in the urine of the researchers exposed is calculated after termination of the exposure and shows half-life times between 1.3 and 2.1 h, and that the dosage absorbed was eliminated within 6 h after exposure.     

A new application of imprinted polymers: Speciation of organotin compounds

Molecular imprinting technology has been employed for the first time to prepare a specifically affinity chromatographic stationary phase for speciation purposes. Tributyltin has been chosen as the template molecule and the non-covalent approach has been applied. Three different polymerization methods have been evaluated: (i) a composite material, (ii) a polymer prepared via-Iniferter grafting; (iii) an emulsion polymer. Columns packed with different polymers have been evaluated by liquid chromatography (LC) coupled to inductively coupled plasma mass spectrometry (ICP-MS). The chromatographic conditions as well as the analytical characteristics of the developed method are discussed in this paper. Our findings have shown formation of specific cavities in the grafted Iniferter as well as in the emulsion polymers with the latter achieving resolution of four organotin compounds. Detection limits are similar to those obtained with commercial, but not specific, stationary phases (6 pg for monobutyltin, MBT; 10 pg for both tributyltin, TBT, and triphenyltin, TPhT; and 20 pg for dibutyltin, DBT). The main advantage of this proposed stationary phase is that good recovery is obtained for all species, including MBT. Baseline resolution for TBT and TPhT has also been obtained. The high selectivity of this column prevents matrix interferences. The method has been validated by analyzing two biota reference materials (ERM-CE477 mussel tissue and T-38 oyster tissue).     

Imidazolinone herbicides in strongly acidic media: Speciation and electroreduction

From UV-visible measurements and potentiometric titrations it follows that the lowest pK values (pK₁) of imidazolinone herbicides correspond to the simultaneous protonation/dissociation equilibria of both the pyridinic (or quinolinic) nitrogen and the carboxyl group, the following pK (pK₂) to the imminium nitrogen and the basic pK (pK₃) to the dissociation of the imido nitrogen. Below pH 6 and down to pH c.a. 2.5, the dominant form of the herbicide is a double ion having both positive and negative charges, this being important in discussing the effect of pH in the natural dynamics of imidazolinone herbicides, especially in their soil sorption. Electrochemical studies of the reduction of the herbicides were made on mercury and carbon electrodes in strongly acidic media (0.1 to 2.7 M H₂SO₄) as well up to pH 7. The reduction signals were all attributed to the reduction of the imidazolinone ring except the second peak/wave that was found to have originated by the reduction of the pyridine/quinoline ring. A signal observed in strongly acidic media and at highly negative overpotentials was attributed to the reduction of the imidazolinone ring of the product of the previous reduction in a process consisting of two reversible electron transfers followed by a protonation reaction.