Oxidation of tertiary polycycl1c amines by RuO4

The reactions of certain tertiary polycyclic amines such as N-benzyl-9-azabicy-clo- [3,3,1]-nonane, N-benzyl-5, 6-dihydro-11H-dibenz [b,e] azepine, and N-benzyl-1,2,3,4-tetrahydroisoquinoline with ruthenium tetroxide, taking place in both heterogeneous and homogeneous systems, have made it possible to establish the order of reactivity of the various methylene groups adjacent to the nitrogen with respect to this oxidizing agent.     

Heteronuclear decoupling interference during symmetry-based homonuclear recoupling in solid-state NMR

We examine the influence of continuous-wave heteronuclear decoupling on symmetry-based double-quantum homonuclear dipolar recoupling, using experimental measurements, numerical simulations, and average Hamiltonian theory. There are two distinct regimes in which the heteronuclear interference effects are minimized. The first regime utilizes a moderate homonuclear recoupling field and a strong heteronuclear decoupling field; the second regime utilizes a strong homonuclear recoupling field and a weak or absent heteronuclear decoupling field. The second regime is experimentally accessible at moderate or high magic-angle-spinning frequencies and is particularly relevant for many realistic applications of solid-state NMR recoupling experiments to organic or biological materials.     

The Suzuki homocoupling reaction under high-intensity ultrasound

The Pd-catalysed Suzuki homocoupling of boronic acids was successfully carried out in water under high-intensity ultrasound (HIU). Heterogeneous catalysis with Pd/C, facilitating work up and purification, could be used without adding phosphine ligands. Reaction rates and yields were strongly influenced by the oxidant employed; excellent results were obtained using either molecular oxygen or 3-bromo-4-hydroxycoumarin. 3-Arylation of the latter with the Suzuki procedure had failed, exclusively affording the homocoupling products, symmetric biaryls. Besides offering a number of operational advantages, the use of HIU broadens the field of application for the Suzuki reaction.     

Chemical modification of chitosan under high-intensity ultrasound

Chitosan (CTS), a biocompatible, biodegradable, non-toxic polymer, dissolves in water only if pH is lowered under 6.5, when a substantial fraction of the amino groups is protonated. Its range of application has been much extended by partially depolymerising it or converting it to water-soluble derivatives. Working under high-intensity ultrasound at 17.8-18.5 kHz, using either a simple horn or a cup horn, we achieved a controlled depolymerization of CTS, also prepared in high yields several derivatives that can be useful intermediates for further chemical modification, as well as several water-soluble derivatives that lend themselves to a host of industrial applications. Compared to conventional methods, all these reactions went to completion in considerably shorter times at lower temperatures.     

Long Term Stability of Proper Rotations of the Perturbed Euler Rigid Body

We study the long term stability of the proper rotations of the perturbed Euler rigid body, in the framework of Nekhoroshev theory. For simplicity we treat here in detail only the kinetically symmetric case (the potential needs not to be symmetric), but we indicate how to extend the results to the triaxial case. We show that the proper rotations around the symmetry axis are Nekhoroshev stable: more precisely, if the initial datum is sufficiently close to a proper rotation, then for a very long time it remains such, and the tip of the unit vector parallel to the angular momentum precesses, up to a small noise, along the level curves of a regular function on the unit sphere. If the proper rotations are resonant, chaotic motions with positive Lyapunov exponents are possible, but chaos (unlike the case of ordinary motions, that is motions not close to proper rotations) is always localized, and does not affect in an essential way the motion of the angular momentum in space. Preliminary numerical results indicate that the theory is, in many aspects, optimal, although in some points it can still be improved.     

A sensitive and specific precursor ion scanning approach in liquid chromatography/electrospray ionization tandem mass spectrometry to detect methylprednisolone acetate and its metabolites in rat urine

A new, simple, sensitive and specific liquid chromatography/electrospray ionization tandem mass spectrometric (LC/ESI‐MS/MS) method in precursor ion scanning (PIS) mode has been developed for the rapid detection of methylprednisolone acetate (MPA) and its metabolites in rat urine. A suitable product ion specific for methylprednisolone (MP) and MPA was selected after a fragmentation study on 20 (cortico)steroids at different collision energies (5–40 eV). Urine samples were simply treated with acetonitrile then dried in a SpeedVac system. The method was validated and compared with other PIS methods for detecting corticosteroids in human urine. It was more sensitive, with limit of detection (LOD) and lower limit of quantitation (LLOQ), respectively, of 5 and 10 ng mL^?1. The method was applied for the analysis of rat urine collected before and after (24, 48, 72 h) intra‐articular (IA) injection of a marketed formulation of MPA (Depo‐Medrol®). MS/MS acquisitions were taken at different collision energies for the precursor ions of interest, detected in PIS mode, to verify the MP‐related structure. Six different metabolites were detected in rat urine, and their chemical structures were assigned with a computational study. Copyright © 2010 John Wiley & Sons, Ltd.     

Composition of Lie transforms with rigorous estimates and applications to Hamiltonian perturbation theory

In this paper we exhibit a rigorous perturbation theory for nearly integrable Hamiltonian systems, based on the composition of Lie Transforms. Precisely, we first study the algorithm for the composition of Lie transforms, and provide rigorous estimates for the convergence radius and the truncation errors of the series; then we use our estimates for a particular model-example, namely a system of weakly coupled harmonic oscillators having Diophantine frequencies, and work out Nekhoroshev-like exponential estimates for the stability times.     

Metal complexes of C2-symmetric chiral bipyridine ligands. X-ray structure of [bis(nitrato)(4S,5S)-2,2-dimethyl-4,5-bis(2-pyridyl)-1,3-dioxolane cobalt(II)]

Chelating properties of C₂-symmetric chiral bipyridine ligands are discussed. In particular we report the syntheses of the cobalt(II), nickel(II), zinc(II) and copper(II) complexes of (4S,5S)-2,2-dimethyl-4,5-bis(2-pyridyl)-1,3-dioxolane. All compounds have been characterized by IR spectroscopy, and an X-ray diffraction analysis has been carried out on one of them: Co(L)(NO₃)₂. The ligand coordinates the cobalt atom by the two nitrogen donors N(1) and N(2). A seven-membered chelation ring is formed, presenting a remarkable non-crystallographic twofold pseudosymmetry around the axis connecting Co and the midpoint of the C(6)–C(7) bond. The metal also binds two monodentate nitrates, thus completing a distorted coordination tetrahedron.     

Riesz transforms for a non-symmetric Ornstein-Uhlenbeck semigroup

Let (ℋ _t ) _t≥0 be the Ornstein-Uhlenbeck semigroup on ℝ ^d with covariance matrix I and drift matrix −λ(I+R), where λ>0 and R is a skew-adjoint matrix and denote by γ _∞ the invariant measure for (ℋ _t ) _t≥0. Semigroups of this form are the basic building blocks of Ornstein-Uhlenbeck semigroups which are normal on L ²(γ _∞). We investigate the weak type 1 estimate of the Riesz transforms for (ℋ _t ) _t≥0. We prove that if the matrix R generates a one-parameter group of periodic rotations then the first order Riesz transforms are of weak type 1 with respect to the invariant measure γ _∞. We also prove that the Riesz transforms of any order associated to a general Ornstein-Uhlenbeck semigroup are bounded on L ^p (γ _∞) if 1<p<∞. The authors have received support by the Italian MIUR-PRIN 2005 project “Harmonic Analysis” and by the EU IHP 2002-2006 project “HARP”.     

A New Indirect Electroanalytical Method to Monitor the Contamination of Natural Waters with 4‐Nitrophenol Using Multiwall Carbon Nanotubes

The electrochemical detection of the hazardous pollutant 4‐nitrophenol (4‐NP) at low potentials, in order to avoid matrix interferences, is an important research challenge. This study describes the development, electrochemical characterization and utilization of a multiwall carbon nanotube (MWCNT) film electrode for the quantitative determination of 4‐NP in natural water. Electrochemical impedance spectroscopy measurements showed that the modified surface exhibits a decrease of ca. 13 times in the charge transfer resistance when compared with a bare glassy carbon (GC) surface. Voltammetric experiments showed the possibility to oxidize a hydroxylamine layer (produced by the electrochemical reduction of 4‐NP on the GC/MWNCT surface) in a potential region which is approximately 700 mV less positive than that needed to oxidize 4‐NP, thus minimizing the interference of matrix components. The limit of detection for 4‐NP obtained using square‐wave voltammetry (0.12 μmol L^?1) was lower than the value advised by EPA. A natural water sample from a dam located in São Carlos (Brazil) was spiked with 4‐NP and analyzed by the standard addition method using the GC/MWCNT electrode, without any further purification step. The recovery procedure yielded a value of 96.5% for such sample, thus confirming the suitability of the developed method to determine 4‐NP in natural water samples. The electrochemical determination was compared with that obtained by HPLC with UV‐vis detection.