A new approach for solving linear bilevel problems using genetic algorithms

Bilevel programming involves two optimization problems where the constraint region of the first level problem is implicitly determined by another optimization problem. This paper develops a genetic algorithm for the linear bilevel problem in which both objective functions are linear and the common constraint region is a polyhedron. Taking into account the existence of an extreme point of the polyhedron which solves the problem, the algorithm aims to combine classical extreme point enumeration techniques with genetic search methods by associating chromosomes with extreme points of the polyhedron. The numerical results show the efficiency of the proposed algorithm. In addition, this genetic algorithm can also be used for solving quasiconcave bilevel problems provided that the second level objective function is linear.     

Macrobicyclic triphosphazides and tri-λ-phosphazenes derived from PhC(CH2PPh2)3. Two propeller-shaped diastereoisomers in the crystals

New macrobicyclic cage-compounds composed of two tripodal, propeller-shaped fragments linked by phosphazide and phosphazene units have been synthesized by reaction of PhC(CH₂PPh₂)₃ with tris(m-azidobenzyl)amines. Two diastereoisomers of one of these cages have been characterized in the solid state by X-ray crystallography, one presenting two propellers with the same sense of twist P^∗,P^∗ whereas in the second one the helical sense of both propellers is the opposite, P^∗,M^∗. In contrast, only one species is apparent in CDCl₃ solution.     

Dimeric self-assembling capsules derived from the highly flexible tribenzylamine skeleton

Tris(m-ureidobenzyl)amines dimerize both in solid state and in solution to give molecular capsules which are able to encapsulate small molecules. The self-assembly was confirmed by crystal X-ray analysis and NMR spectroscopy. The X-ray structure showed the encapsulation of one molecule of CH(2)Cl(2). This new type of capsules presents a propeller-like topology and a belt of six hydrogen-bonded ureas. Encapsulation studies in solution and heterodimerization processes are also disclosed.     

New Models for the Study of the Racemization Mechanism of Carbodiimides. Synthesis and Structure (X-ray Crystallography and (1)H NMR) of Cyclic Carbodiimides

The crystal and molecular structure of carbodiimides 2 (5,6,18,19-tetradehydro-5,12,13,18,25,26-hexahydrotetrabenzo[d,h,m,q][1,3,10,12]tetraazacyclooctadecine) and 3 (8,10,22,24-tetraazapentacyclo[23.3.1.1(3,7).1(11,15).1(17,21)]dotriaconta-1(29),3,5,7(32),8,9,11,13,15(31),17,19,21(30),22,23,25,27-hexadecaene) have been determined. The activation barriers for the racemization of carbodiimides 1 (6,7-dihydrodibenzo[d,h][1,3]diazonine), 2, and 3 have been determined. While 1 presents a relatively high barrier (17.4 kcal mol(-)(1)), 2 and 3 have very low activation barriers (between 5 and 7 kcal mol(-)(1)). We tentatively conclude that open-chain and large-ring carbodiimides racemize by nitrogen inversion or trans-rotation while medium-size cyclic carbodiimides racemize by cis-rotation.     

A tandem-flow assembly for the chemiluminometric determination of hydroquinone

A direct chemiluminescent procedure for determination of hydroquinone based on the emergent flow methodology known as multicommutation or tandem-flow is presented for first time. The manifold was based on a set of three channels and three solenoid valves; and, the determination was performed at 60 °C and at flow-rate of 7.5 ml min⁻¹. The complete cycle lasted 35 s, which resulted in a sample flow trough of 103 h⁻¹. The chemical process was the hydroquinone oxidation with the system sulphuric acid-potassium permanganate; and the light emission was clearly enhanced by the presence of quinine sulphate and benzalkonium chloride reaching a detection limit of 30 μg l⁻¹. The dynamic interval was over the range 0.1-15.0 mg l⁻¹ and a large list of interferents were assayed; the chemical robustness was also tested. The method was applied to different type of samples: namely, pharmaceutical formulations, a photographic solution and irrigation and residual superficial waters.     

The Molecular Structure and NMR Properties of P-Phosphinoylmethyl Aminophosphonium Salts

The molecular structures of two aminophosphonium salts (bromide and tetrafluoroborate) have been determined by X-ray analysis. They have similar conformations and hydrogen bond (HB) networks: the N–H acid proton is bonded to the anion and, in the case of the fluoroborate, to the oxygen atom of the phosphine oxide, forming a pseudo six-membered ring closed by a weak N–HO intramolecular hydrogen bond (IMHB). These compounds have been studied by multinuclear NMR in solution, including the ¹⁵N-labeled derivatives, to determine a complete set of coupling constants. A coupling of 1.5 Hz between the ¹⁵N and the ³¹P nuclei, separated by three bonds, was observed experimentally for the bromide in CDCl₃ solution, which appears to be a classical ³ J _N-P across the covalent bonds and not a ^3h J _N-P across the IMHB.     

Scanning electron microscopy of legs of two species of sucking lice (Anoplura: Phthiraptera)

Pretarsal, tarsal and tibial structures of the forelegs, midlegs and hindlegs of Pediculus humanus of humans and of Haematopinus apri Goureau, 1866 (Phthiraptera), a parasite of feral hogs, were studied using light microscopy and scanning electron microscopy. Details of the tibial thumb-like process (tl) with the spine of the thumb (spn), tarsal apophysis (ta) and the coupled finger-like process (cfl) can be observed in the leg photomicrograph of both species. A frontal view of the leg in open position shows the articulation of the claw: the structures of an open-closed system, a tooth row (te), rack-system (rs) and two telescopic columns (tc) which are present near the base of the claw in both species. In H. apri, we observed a pad-like structure, the flap-like tibial lobe (fl) on the ventral surface on the tarsus, the euplantulae, with several sensilla basiconica, which is present in each leg.     

The use of laser-induced plasma spectroscopy technique for the characterization of boiler tubes

The present work focuses on the characterization of boiler tube walls using laser-induced plasma spectroscopy technique with visual inspection by optical and scanning electron microscopy of the cross-sections of these tubes. In a watertube boiler, water runs through tubes that are surrounded by a heating source. As a result, the water is heated to very high temperatures, causing accumulation of deposits on the inside surfaces of the tubes. These deposits play an important role in the efficiency of the boiler tube because they produce a reduction of the boiler heat rate and an increase in the number of tube failures. The objectives are to determine the thickness and arrangement of deposits located on the highest heat area of the boiler and compare them with tube parts where the heat flux is lower. The major deposits found were copper and magnetite. These deposits come mainly from the boiler feedwater and from the reaction between iron and water, and they do not form on the tube walls at a uniform rate over time. Their amount depends on the areas where they are collected. A Nd:YAG laser operating at 355 nm has been used to perform laser-induced plasma spectra and depth profiles of the deposits.     

LIPS and linear correlation analysis applied to the classification of Roman pottery Terra Sigillata

Archaeological ceramics Terra Sigillata manufactured in different production centres have been studied by laser-induced plasma spectroscopy (LIPS). The aim of this work was to establish a procedure for the rapid classification of these archaeological ceramics in function of their provenance through combination of LIPS and statistical methodologies. Representative emission spectra of the Hispanic, Gaulish and African groups of pottery were selected as references. The use of linear correlation allowed one to cluster the samples by quantitative comparison of LIP spectra, leading to a reliable assignment of Terra Sigillata pieces to origin centres. PACS 42.62.Fi; 32.30.Jc; 02.50.-r; 81.05.Je