Trajectories Joining Two Submanifolds under the Action of Gravitational and Electromagnetic Fields on Static Spacetimes

In this paper we present existence and multiplicity results for orthogonal trajectories joining two submanifolds under the action of gravitational and electromagnetic fields on static spacetimes. These trajectories are critical points of unbounded functionals and they can be found by using a variant of the saddle point theorem and the relative category theory.     

Rapid and direct analysis of gamma-hydroxybutyric acid in urine by capillary electrophoresis-electrospray ionization ion-trap mass spectrometry

The present work was aimed at the development of a capillary electrophoretic analysis of gamma-hydroxybutyric acid (GHB) using electrospray ion trap mass spectrometry to achieve the direct and unequivocal detection of this analyte in human urine. Optimized capillary electrophoretic conditions were: injection, 20 s at 0.5 psi (1 psi = 6894.76 Pa); buffer electrolyte, 12.5 mM ammonium formate adjusted to pH 8.35 with diethylamine; fused silicacapillary: 100 cm x 50 microm i.d.; separation voltage, 25 kV (forward polarity) + 0.5 psi; room temperature. Electrospray and mass spectrometric conditions were: drying gas and nebulizing gas (nitrogen) at flow rate 3 l/min, temperature 250 degrees C, nebulizer pressure: 10 psi; sheath liquid solution: methanol-water (90:10) containing 0.1% ammonia delivered at 3 microl/min; spray voltage 3.5 kV. Mass spetrometric detection was carried out in the selected ion monitoring mode of negative molecular ions at 103 m/z for GHB and 115 m/z for maleic acid (I.S.). Under these conditions the baseline separation of GHB and the I.S. was obtained. The selectivity of the analysis allowed for direct injection of unextracted urine, previously diluted 1:4 with water. Linearity was assessed in the GHB concentration range from 80 to 1280 microg/ml in urine. Analytical sensitivity (as limit of detection) resulted about 5 microg/ml in water and 20 microg/ml in original urine. Analytical precision was fairly acceptable with R.S.D. values lower than 5% for migration times and 18% for quantitation in real samples, in both intra day and day-to-day experiments. On these grounds, the developed method can be adopted for rapid identification of acute intoxications from GHB in humans.     

Asymmetric synthesis of an N-acylpyrrolidine for inhibition of HCV polymerase

A practical asymmetric synthesis of a highly substituted N-acylpyrrolidine on multi-kilogram scale is described. The key step in the construction of the three stereocenters is a [3+2] cycloaddition of methyl acrylate and an imino ester prepared from l-leucine t-butyl ester hydrochloride and 2-thiazolecarboxaldehyde. The cycloaddition features novel asymmetric catalysis via a complex of silver acetate and a cinchona alkaloid, particularly hydroquinine, with complete diastereomeric control and up to 87% enantiomeric control. The alkaloid serves as a ligand as well as a base for the formation of the azomethine ylide or 1,3-dipole. Experiments have shown that the hydroxyl group of hydroquinine is a critical element for the enantioselectivities observed. The cycloaddition methodology is also applicable to methylvinyl ketone, providing access to either alpha- or beta-epimers of 4-acetylpyrrolidine depending on the reaction conditions utilized. The synthesis also highlights an efficient N-acylation, selective O- versus N-methylation, and a unique ester reduction with NaBH4-MeOH catalyzed by NaB(OAc)3H that not only achieves excellent chemoselectivity but also avoids formation of the undesired but thermodynamically favored epimer. The highly functionalized target is synthesized in seven linear steps from l-leucine t-butyl ester hydrochloride with all three isolated intermediates being highly crystalline.     

A New Photoactivatable Ruthenium(II) Complex with an Asymmetric Bis-Thiocarbohydrazone: Chemical and Biological Investigations

The synthesis, photoactivation and biological activity of a new piano-stool Ru(II) complex is herein reported. The peculiarity of this complex is that its monodentate ligand which undergoes the photodissociation is an asymmetric bis-thiocarbohydrazone ligand that possesses a pyridine moiety binding to Ru(II) and the other moiety contains a quinoline that endows the ligand with the capacity of chelating other metal ions. In this way, upon dissociation, the ligand can be released in the form of a metal complex. In this article, the double ability of this new Ru(II) complex to photorelease the ligand and to chelate copper and nickel is explored and confirmed. The biological activity of this compound is studied in cell line A549 revealing that, after irradiation, proliferation inhibition is reached at very low half maximal inhibitory concentration (IC₅₀) values. Further, biological assays reveal that the dinuclear complex containing Ni is internalized in cells.     

Physical Characterization of Blends Based on Liquid Crystalline Polyesters and Amorphous Polymers

In this work the effect of the inclusion of low percentages of theliquid crystal polymer PET/PHBGO on the rheological and mechanical behaviour of Polycarbonate is described.     

Complex palytoxin‐like profile of Ostreopsis ovata. Identification of four new ovatoxins by high‐resolution liquid chromatography/mass spectrometry

Over the past decades, Italian coastlines have been plagued by recurring presence of the benthic dinoflagellate Ostreopsis ovata. Such an alga has caused severe sanitary emergencies and economic losses due to its production of palytoxin‐like compounds. Previous studies have confirmed the presence of ovatoxin‐a (OVTX‐a) as the major toxin of the algal toxin profile together with small amounts of putative palytoxin (PLTX). In our ongoing research on O. ovata toxins we report herein on in‐depth investigation of an O. ovata culture carried out by high‐resolution (HR) liquid chromatography/mass spectrometry (LC/MS) and tandem mass spectrometry (MS²). Particularly, the presence of putative PLTX and OVTX‐a was confirmed and the occurrence in the extract of four new palytoxin‐like compounds, OVTX‐b, ‐c, ‐d, and ‐e, was highlighted. Elemental formulae have been assigned to the new ovatoxins and information has been gained about their structural features. A quantitative study of the O. ovata culture extract indicated that the whole of the new ovatoxins represents about 46% of the total toxin content and, thus, their presence has to be taken into account when LC/MS‐based monitoring programs of either plankton or contaminated seafood are carried out. Copyright © 2010 John Wiley & Sons, Ltd.     

Convex domains of Finsler and Riemannian manifolds

A detailed study of the notions of convexity for a hypersurface in a Finsler manifold is carried out. In particular, the infinitesimal and local notions of convexity are shown to be equivalent. Our approach differs from Bishop??s one in his classical result (Bishop, Indiana Univ Math J 24:169?C172, 1974) for the Riemannian case. Ours not only can be extended to the Finsler setting but it also reduces the typical requirements of differentiability for the metric and it yields consequences on the multiplicity of connecting geodesics in the convex domain defined by the hypersurface.     

Automated detection and characterization of graphene and few‐layer graphite via Raman spectroscopy

Several processes have to be automated in order to use graphene in future industrial applications. One of these is the detection and characterization of graphene and few‐layer graphite (FLG) flakes on a substrate. Raman spectroscopy is an ideal tool for this purpose, as it allows not only the identification of these graphitic materials on arbitrary substrates but also monitoring the quality of flakes within the sample. In this paper, we report how graphene and FLG crystallites can be automatically detected and characterized by monitoring the evolution of Raman bands. We present an algorithm that achieves this purpose and thus has special potential in industrial applications of graphene. Copyright © 2010 John Wiley & Sons, Ltd.     

Expedient synthesis of pseudo-Pro-containing peptides: towards constrained peptidomimetics and foldamers

The reaction of sulfonyl peptides containing L- or D-configured Ser or Thr with bis(succinimidyl) carbonate in the presence of a catalytic amount of a base affords, in solution or in the solid phase, the corresponding peptides with one or two, consecutive or alternate oxazolidin-2-ones (Oxd). The Oxd ring can be regarded to as a pseudo-Pro with an exclusively trans conformation of the preceding peptide bond; homochiral Oxd-containing peptides adopt extended conformations, while the presence of a D-configured Oxd favours folded conformations.