Rate of Convergence of Generalized Hermite–Padé Approximants of Nikishin Systems

We study the rate of convergence of interpolating simultaneous rational approximations with partially prescribed poles to so-called Nikishin systems of functions. To this end, a vector equilibrium problem in the presence of a vector external field is solved which is used to describe the asymptotic behavior of the corresponding second-type functions which appear.     

Orientational effect of the phenylsulfonyl group in the thermal spiroketalization of dihydroxyketone equivalents

The thermal cyclization of a dihydroxyketone equivalent 4b leads to the predominant formation of crystalline 4-(benzenesulfonyl)-1,6-dioxaspiro[4.5]decane ( 8 ). Under similar reaction conditions the tetrahydrofuranylidene derivative 6 is obtained from ketone 4c . It does appear that the phenylsulfonyl group is a factor which influences the course of the reaction leading to the preferential formation of one of the possible stereoisomers.     

Levels of polycyclic aromatic hydrocarbons,polychlorinated byphenyls,methylmercury and butyltins in the natural UNESCO reserve of the biosphere of Urdaibai (Bay of Biscay,Spain)

Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), methylmercury (MeHg⁺) and butyltins (mono-, di- and tri-butyltin, MBT, DBT and TBT) were monitored in oysters (Crassostrea sp.) and sediments collected in different sampling points of the UNESCO reserve of the biosphere of Urdaibai (Bay of Biscay) from March 2006 to June 2007. In the case of oyster samples, concentrations in the 290–1814 µg kg^?1 (PAHs), 70–475 µg kg^?1 (PCBs), 75–644 µg kg^?1 (MeHg⁺) and 200–1300 µg kg^?1 (as a sum of the three butyltins) ranges were obtained. In most samples TBT was the most abundant butyltin, followed by DBT and MBT. It should be highlighted that most samples exceeded the highest range (367 µg kg^?1) found in the last mussel watch programme carried out by the National Oceanic and Atmospheric Administration (NOAA) for butyltins in oyster samples. This could be due to the presence of a shipyard in the estuary. Sediment concentrations ranged as follows: total PAHs (856–3495 µg kg^?1) and total PCBs (58–220 µg kg^?1). Organometallic species were always below the limits of detection (LODs) (0.24 µg kg^?1 for MeHg⁺, 0.6 µg kg^?1 for MBT, 0.48 µg kg^?1 for DBT and 1.1 µg kg^?1 for TBT). In both sediment and oyster PAH sources were mostly combustion. In the case of PCBs, 4-6 chlorine-atom congeners were the most abundant ones. Slight differences in the profile of PAHs as well as PCBs can be detected when the matrices were compared with each other. Finally, in the case of PAHs, sediment and water column played the main role in the accumulation pathway into the organisms in all the sampling stations.     

PHOTOPHYSICAL BEHAVIOUR OF 5-METHOXYPSORALEN IN DIOXANE-WATER MIXTURES

Abstract— Triplet-triplet absorption spectra, intersystem crossing quantum yields, fluorescence lifetimes, and fluorescence quantum yields of 5-methoxypsoralen (5MOP) in dioxane-water mixtures are reported. The fluorescence and triplet formation quantum yields depend strongly on the water content in the mixtures, increasing up to maximum values which are, respectively, twentyfold and fivefold larger than in dioxane and then decreasing. This behaviour is essentially due to the variation of the internal conversion rate constant. With these solvent mixtures it is possible to emulate the dielectric response of 5MOP photophysical parameters in other media, such as in biological model systems and in human blood lipoproteins. The biological importance of these results is discussed.     

New heterocyclic derivatives of 1′- and 3′-amino-5′,6′,7′,8′-tetrahydro-2′-acetonaphthones

The preparation of 1′-and 3′-amino-5′,6′,7′,8′-tetrahydro-2′-acetonaphthones (IIIa and IIIb) is described, by reduction of the low temperature nitration products of 5′,6′,7′,8′-tetrahydro-2′-acetonaphtone (I). The structures of the nitro isomers (IIa and IIb), and the reduction products, IIIa and IIIb, were elucidated spectroscopically. By known reactions, a series of new heterocyclic compounds prepared from the o-aminoketones, IIIa and IIIb, resulted in two series of new heterocyclic compounds.     

Thermodynamic study of functionalized calix[n]arene and resorcinol[n]arene monolayers spreaded at an aqueous pendant drop

The behavior of insoluble calix[n]arene and resorcinol[n]arene derivatives monolayers were studied through the use of a constant surface Langmuir balance based on Axisymmetric Drop Shape Analysis (ADSA). In each case, a stable monolayer was obtained and different transitions (induced for lateral compression) could be identified. Thermodynamic parameters were computed through two dimensional Clausius–Clayperon equations and used to valuate the monolayer stability. A noticeable reduction of thermodynamic parameters occurred at highly tested temperatures (328 and 338 K) for those compounds that had hydrocarbon tails or benzene rings attached to one side of macrocyclic rim. Such fact was related to a monolayer rearrangement where the macrocyclic ring changed from a parallel to a perpendicular orientation. In this orientation the hydrophobic interactions between hydrocarbon chains and benzene rings were maximized. At highly temperature, where vigorous molecular motion existed, those interactions were superior to the stabilization effect through hydrogen bond.     

Ruthenium(III) and iridium(III) complexes with nicotine

A new chloride-dimethylsulfoxide-ruthenium(III) complex with nicotine trans-[Ru^IIICl₄(DMSO)[H-(Nicotine)]] (1) and three related iridium(III) complexes; [H-(Nicotine)]trans-[Ir^IIICl₄(DMSO)₂] (2), trans-[Ir^IIICl₄(DMSO)[H-(Nicotine)]] (3) and mer-[Ir^IIICl₃(DMSO)(Nicotine)₂] (4) have been synthesized and characterized by spectroscopic techniques and by single crystal X-ray diffraction (1, 2, and 4). Protonated nicotine at pyrrolidine nitrogen is present in complexes 1 and 3 while two neutral nicotine ligands are observed in 4. In these three inner-sphere complexes coordination occurs through the pyridine nitrogen. Moreover, in the outer-sphere complex 2, an electrostatic interaction is observed between a cationic protonated nicotine at the pyrrolidine nitrogen and the anionic trans-[Ir^IIICl₄(DMSO)₂]^¯ complex.     

Effect of applied bias voltage on corrosion-resistance for TiC1−xNx and Ti1−xNbxC1−yNy coatings

Corrosion-resistance behavior of titanium carbon nitride (Ti-C-N) and titanium niobium carbon nitride (Ti-Nb-C-N) coatings deposited onto Si(1 0 0) and AISI 4140 steel substrates via r.f. magnetron sputtering process was analyzed. The coatings in contact with a solution of sodium chloride at 3.5% were studied by Tafel polarization curves and impedance spectroscopy methods (EIS). Variations of the bias voltage were carried out for each series of deposition to observe the influence of this parameter upon the electrochemical properties of the coatings. The introduction of Nb in the ternary Ti-C-N film was evaluated via X-ray diffraction (XRD) analysis. The structure was characterized by using Raman spectroscopy to identify ternary and quaternary compounds. Surface corrosion processes were characterized using optical microscopy and scanning electron microscopy (SEM). XRD results show conformation of the quaternary phase, change in the strain of the film, and lattice parameter as the effect of the Nb inclusion. The main Raman bands were assigned to interstitial phases and “impurities” of the coatings. Changes in Raman intensities were attributed to the incorporation of niobium in the Ti-C-N structure and possibly to resonance enhancement. Finally, the corrosion data obtained for Ti-C-N were compared with the results of corrosion tests of Ti-Nb-C-N coating. The results obtained showed that the incorporation of niobium to Ti-C-N coatings led to an increase in the corrosion-resistance. On another hand, an increase in the bias voltage led to a decrease in the corrosion-resistance for both Ti-C-N and Ti-Nb-C-N coatings.     

A DNA-binding copper(I) metallosupramolecular cylinder that acts as an artificial nuclease

The DNA binding of a dicationic pyridylimine-based dicopper(I) metallosupramolecular cylinder is reported together with its ability to act as an artificial nuclease. The cylinder binds strongly to DNA; more strongly than the spherical dication [Ru(phen)(3)](2+) (phen=1,10-phenanthroline), but more weakly than the corresponding tetracationic cylinders. DNA coiling effects are not observed with this dication, in contrast to the situation with the previously reported tetracationic cylinder involving a similar ligand. Linear dichroism (LD) data suggests that the dicopper cylinder binds in a different orientation from that of the tetracationic iron cylinder. Furthermore, the dicopper cylinder shows DNA-cleavage activity in the presence of peroxide. Of particular note is that the cylinder displays a marked and unusual ability to cleave both DNA strands at the same site, probably reflecting its dinuclear nature and possibly its mode of binding to the DNA.