Identification and assay of wild-type and modified nucleoside mixtures by turbo ionspray ionization tandem mass spectrometry

A method is presented which allows the identification and assay of a nucleoside in the presence of other analogues and homologues. The method is based on the conventional multiple reaction monitoring approach performed on the [M + H]+ ions of wild-type and modified nucleosides produced by the turbo ionspray ionization method on a triple-quadrupole mass spectrometer. The accuracy of the quantitative determination relies on the evaluation of a response factor rho, which takes into account the kinetics of dissociation of the parent ions into the protonated [B + 2H]+ nucleobase ions. The evaluation of the absolute concentration of each analyte in the examined mixture does not require any previous chromatographic separation.     

Ternary complexes between cationic GdIII chelates and anionic metabolites in aqueous solution: an NMR relaxometric study

The (1)H and (17)O NMR relaxometric properties of two cationic complexes formed by Gd(III) with a macrocyclic heptadentate triamide ligand, L(1), and its Nmethylated analogue, L(2), have been investigated in aqueous media as a function of pH, temperature and magnetic field strength. The complexes possess two water molecules in their inner coordination sphere for which the rate of exchange has been found to be sensibly faster for the Nmethylated derivative and explained in terms of electronic effects (decrease of the charge density at the metal center) and perturbation of the network of hydrogen-bonded water molecules in the outer hydration sphere. The proton relaxivity shows a marked dependence from pH and decreases of about six units in the pH range 6.5 to 9.0. This has been accounted for by the displacement of the two water molecules by dissolved carbonate which acts as a chelating anion. The formation of ternary complexes with lactate, malonate, citrate, acetate, fluoride and hydrogenphosphate has been monitored by (1)H NMR relaxometric titrations at 20 MHz and pH 6.3 and the value of the affinity constant, K, and of the relaxivity of the adducts could be obtained. Lactate, malonate and citrate interact strongly with the complexes (log K > or =3.7) and coordinate in a bidendate mode by displacing both water molecules. Larger affinity constants have been measured for GdL(2). Acetate, fluoride and hydrogenphosphate form monoaqua ternary complexes which were investigated in detail with regard to their relaxometric properties. The NMR dispersion (NMRD) profiles indicate a large contribution to the relaxivity of the adducts from water molecules belonging to the second hydration shell of the complexes and hydrogen-bonded to the anion. A VT (17)O NMR study has shown a marked increase of the rate of water exchange upon binding which is explained by coordination of the anion in an equatorial site, thus leaving the water molecule in an apical position, more accessible for interactions with the solvent molecules of the second hydration shell which facilitate the exchange process.     

Regularity results for positive solutions of a semilinear elliptic system

Let , N≧3 be an open set. In this paper we study weak positive solutions of the following semilinear system where p≧1, q≧1, with pq>1, and u∈L^q(Ω), v∈L^p(Ω), and we give in particular some regularity results. Furthermore, we give some applications to the biharmonic equation. Entrata in Redazione il 25 febbraio 1999.     

Gaussian Limiting Behavior of the Rescaled Solution to the Linear Korteweg–de Vries Equation with Random Initial Conditions

We analyze the asymptotic behavior of the rescaled solution to the linear Korteweg–de Vries equation when the initial conditions are supposed to be random and weakly dependent. By means of the method of moments we prove the Gaussianity of the limiting process and we present its correlation function. The same technique is applied to the analysis of another third-order heat-type equation.     

Carbon linear chains inside multiwalled nanotubes

Multiwalled carbon nanotubes have been deposited on graphite cathodes by using an arc discharge technique in He atmosphere, with the insertion of a catalytic Ni-Cr mixture as well as without catalysers. The topography of such deposition has been investigated by SEM, while a parallel micro-Raman study has revealed, in particular regions of the deposited cathodes, strong bands in the range 1780-1860 cm⁻¹, assignable to linear carbon chains inside the nanotubes. The variation of intensity, frequency and bandwidth of such bands has been investigated, in relation with the spectral characters of the host multiwalled carbon nanotube. In the cathode deposited without catalyst a quite ordered configuration of multiwalled carbon nanotubes is obtained in the central zone, while the maximum concentration of linear carbon chains is found in a ring shaped zone just inside the border. In sample obtained with catalyst the deposited multiwalled carbon nanotubes appear always more disordered, and a remarkable concentration of carbon chains appears in some zones, with a more casual distribution.     

Bessel functions of third order and the distribution of cyclic planar motions with three directions

The exact distribution of a cyclic planar motion with three directions is explicitly derived in terms of Bessel functions of order three (suitably combined). The absolutely continuous part of the distribution is proved to satisfy suitable boundary conditions and some of its properties are analyzed. The transformations converting the governing equations of order three is presented and its solutions (used here) derived by applying the Frobenius method.     

Formula di Cauchy (n+1)-dimensionale per le funzioni analitiche din variabili complesse

Ad Andreas Speiser nel suo 60^o compleanno. Anmerkung der Redaktion. Die vorliegende Arbeit war für die Festschrift Andreas Speiser, Orell Füssli, 1945, berechnet. Wegen versp?tetem Eintreffen konnte sie leider nicht mehr in diese aufgenommen werden.     

Reactivity of lithium 2,3-dihydro-1-benzothiophene-1-oxide toward aldehydes and imines and DFT calculations

The sulfinyl carbanion derived from 2,3-dihydro-1-benzothiophene-1-oxide and its lithium salt has been investigated by DFT calculations. The lithium carbanion was treated with aldehydes and imines to give chiral hydroxy and amino derivatives, with high stereoselectivity at the carbon α to the sulfoxide group (trans diastereoisomers), but with low diastereoselectivity at the hydroxyl or amine group. DFT calculations were used to rationalize the different stereochemical behavior of cyclic and acyclic lithiated sulfoxides in the reaction with aldehydes and azomethines.