Anharmonic effects in large-amplitude vibrations of metal clusters

Two types of extreme collective motion, large-amplitude many-phonon vibration of the ionic core and rotation of the cluster with high angular momenta, are considered. The interplay between vibration and collective motion towards fission is discussed. A new mechanism of formation and rupture of the neck is proposed which is based on the Franck-Condon principle, and accounts for the interplay between vibration and fission. Under rotation, the change of the shape of the cluster and a phase transition from axially symmetric to triaxial ellipsoid are predicted. For studying the effects, vibrational motion can be induced by laser radiation. Rotational motion may arise in collisions of clusters. Received 26 April 2001 and Received in final form 15 October 2001     

Reaction of 1,3-dimethyl-5-acetyl-barbituric acid (DAB) with primary amines. Access to intermediates for selectively protected spermidines

The ability of 1,3-dimethyl-5-acetyl-barbituric acid (DAB) to react with primary amines in a chemoselective fashion was applied to the synthesis of a selectively protected spermidine.     

A new technique for obtaining the activation energy distribution of a relaxing system

This paper describes a robust and fast fitting procedure applicable for relaxing processes that cannot be understood as a discrete sum of single processes but require an activation energy distribution. The method is based on a set of closed-form expressions that allow the computation of the relaxation parameters directly from the isochronal curves obtained experimentally. The usefulness of this method is checked by analyzing the isochronal curves given by a theoretical energy distribution and the magnetic disaccommodation spectra observed in yttrium iron garnet (YIG) samples. PACS 02.60.Ed; 75.60.Lr; 75.50.Gg     

A novel strategy to verification of adulteration in alcoholic beverages based on Schlieren effect measurements and chemometric techniques

A novel strategy to evaluation of adulteration in alcoholic beverages based on the measurement of the Schlieren effect using an automated FIA system with photometric detection is proposed. The assay is based on the Schlieren effect produced when beverage samples are injected in a single-line FIA system that uses water as carrier stream and a light-emitting diode-phototransistor photometer controlled by microcomputer as detector. The flow system presents limited mixing conditions which make possible to create gradients of refractive index (Schlieren effect) in the injected sample zone. These gradients are reproducible, characteristic of each alcoholic beverage and undergo specific modifications when adulterations with water or ethanol are imposed. Schlieren effect data of brandies, cachaças, rums, whiskies and vodkas were treated by SIMCA to elaborate class models applied in the evaluation of alcoholic beverages adulteration. Samples of the original matrix of each sort of beverages were adulterated in laboratory by adding water, methanol and ethanol in levels of 5% and 10% (v/v). These samples were used as test set to validate SIMCA class models. The verification of authenticity using Schlieren effect measurements presented good results making possible to identify 100% of the beverages samples adulterated in laboratory and 93% of the actual adulterated alcoholic beverages with confidence levels of 95%. As principal advantage, the automated system does not use reagents to carry out the analysis.     

Carrier diffusion in InGaAs/GaAs quantum wells grown on vicinal GaAs(0 0 1) substrates

We have investigated the influence of vicinal GaAs substrates on the optical and electronic properties of InGaAs/GaAs quantum wells (QWs). A single In_0.10Ga_0.90As QW was grown by molecular-beam epitaxy on a vicinal GaAs(0 0 1) substrate with a miscut angle of 0° (nominal), 2°, 4° and 6° towards [1 1 0]. The carrier diffusion was obtained by a micro-photoluminescence scan technique that permits to observe the effective diffusion length characterized by the lateral spread of carriers in the QW followed by radiative recombination. The carrier diffusion length was obtained parallel (L_||) and perpendicular (L) to the atomic steps. The diffusion length decreases as the temperature increases up to 100 K. Above this temperature we found different behaviours that depend on the sample miscut angle.     

Perfect fluid spacetimes admitting curvature collineations

Some basic concepts about curvature collineations are reviewed and the existing results on this topic are applied to the case of perfect fluids, giving a characterization of those amongst them which admit proper curvature collineations.     

On γ-hyperelliptic Numerical Semigroups

This work was realized while the author was ICTP (Trieste - Italy) with a grant from the International Atomic Energy Agency and UNESCO.     

Development and critical comparison of greener flow procedures for nitrite determination in natural waters

Two greener procedures for flow-injection spectrophotometric determination of nitrite in natural waters were developed and critically compared. Replacement of toxic reagents, waste minimization and treatment were exploited to attend the standards of clean chemistry. The flow system was designed with solenoid micro-pumps in order to minimize reagent consumption and waste generation. The first procedure is based on the Griess diazo-coupling reaction with sulfanilamide and N-(1-naphthyl)ethylenediamine (NED) yielding an azo dye, followed by photodegradation of the low amount of waste generated based on the photo-Fenton reaction. The second procedure is based on the formation of iodine from nitrite and iodide in acid medium in order to avoid the use of toxic reagents. For Griess method, linear response was achieved up to 1.0 mg L^− 1, described by the equation A = − 0.007 + 0.460C (mg L^− 1), r = 0.999. The detection limit was estimated as 8 μg L^− 1 at the 99.7% confidence level and the coefficient of variation was 0.8% (n = 20). The sampling rate was estimated as 108 determinations per hour. The consumption of the most toxic reagent (NED) is reduced 55-fold and 20-fold in comparison to batch method and flow injection with continuous reagent addition, respectively. A colorless residue was obtained by in-line photodegradation with reduction of 87% of the total organic carbon content. The results obtained for natural water samples were in agreement with those achieved by the reference method at the 95% confidence level. For the nitrite–iodide method, linear response was observed up to 2.0 mg L^− 1, described by the equation A = − 0.024 + 0.148C (mg L^− 1), r = 0.999. The detection limit was estimated as 25 μg L^− 1 at the 99.7% confidence level and the coefficient of variation was 0.6% (n = 20). The sampling rate was estimated as 44 determinations per hour. Despite avoiding the use of toxic reagents, the nitrite–iodide method presented worst performance in terms of selectivity and sensitivity.