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”.     

Co dissociation and recombination reactions on Ni(100)

The kinetics of atomic carbon and oxygen buildup on a Ni(100) surface exposed to carbon monoxide at high temperatures have been investigated by Auger electron spectroscopy. The experimental data, taken at different sample temperatures (453 , T 573 K) and at different CO partial pressures (3 ×10⁻⁷ , P_co , 3 ×10⁻¹ mbar) allowed the identification of the CO dissociation mechanism. By fitting the experimental data with a set of rate equations describing CO dissociation, CO reduction of surface oxygen, and C and O recombination, we have been able to determine the pre-exponential factors and the activation energies of these processes.     

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.     

N-propargylic beta-enaminones: common intermediates for the synthesis of polysubstituted pyrroles and pyridines.

N-Propargylic beta-enaminones have been used as common intermediates for the synthesis of polysubstituted pyrroles and pyridines. Best results have been obtained using DMSO as solvent. In the presence of Cs(2)CO(3) N-propargylic beta-enaminones are cyclized to pyrroles in good to high yields, whereas omitting bases and using CuBr leads to the selective formation of pyridines.     

Water-Chain intervention in the ketonization of vinyl alcohol. An ab initio study

The ketonization of vinyl alcohol in aqueous solution has been studied by means of ab initio calculations, using the STO -3G basis set. The intervention of a chain of two water molecules reduces dramatically the potential barrier. This result agrees with experimental facts.