Aromatic substitution in the complexes formed upon addition of gaseous arenium ions to proelectrophiles. A FT-ICR study

Experiments based on FT-ICR mass spectrometry provide conclusive evidence for the operation of an alternative mechanism of electrophilic aromatic substitution occurring within the complex formed upon addition of gaseous arenium ions to a variety of proelectrophiles, including alkyl halides, alcohols, epoxides, esters and diazoalkanes. The factors affecting the efficiency of the unconventional substitution are examined in the light of the kinetic results of the FT-ICR experiments.     

Minimum blocking configurations

Some results on configurations realizing minimum blocking sets of a finite projective plane are obtained by introducing a suitable attraction property.Dedicated to Professor M. Scafati Tallini on the occasion of her 65th birthday     

Determination of low levels of free fibres of chrysotile in contaminated soils by X-ray diffraction and FTIR spectroscopy

A new analytical method for the determination of low levels (0.01–1 wt%) of free fibres of chrysotile in contaminated clayey, sandy and sandy-organic soils is described. The detection limit of 0.01 wt% is reached with an enrichment of free fibres of chrysotile in the sample using a standard laboratory elutriator for sedimentation analysis. The chrysotile quantitative determination is performed both by X-ray powder diffraction, using the internal standard and reference intensity ratio methods, and by Fourier-transform infrared absorption spectroscopy. The procedure can be successfully applied to different soils after removal, by a thermal treatment, of the matrix components which can interfere. This straightforward method fulfils the request of public institutions and private companies for an appropriate quantitative determination of chrysotile-free fibres in contaminated soils.     

The magnetic behaviour of [NnBu4]4[Ni16Pd16(CO)40]: an even-electron homoleptic carbonyl-metal cluster anion displaying a J = 2 ground state

The magnetic behaviour of the even-electron [Ni16Pd16(CO)40]4- cluster, in its [NnBu4]+ salt, has been investigated by magnetometry and muon spin rotation/relaxation (muSR) spectroscopy. The susceptibility measurements show an exceptionally high magnetic moment corresponding to a total spin value J=2. This suggests a Hund filling of a quadruplet ground state, quite unique in carbonyl-metal clusters. SQUID magnetometry shows a departure from the Curie-Weiss law, for T>150 K, and strong deviation from a Brillouin behaviour of the magnetisation curves. muSR spectroscopy in zero applied field shows a temperature independent decay of the muon spin polarisation, similar to that of a purely paramagnetic system. The observed muon spin repolarisation in a moderate external longitudinal field, however, invalidates this simple picture and suggests the presence of a local anisotropy field acting on the cluster's magnetic moment. A consistent interpretation of magnetometry and muSR results implies the occurrence of an additional interaction of the cluster spin with an effective crystalline field. The inclusion of this interaction in a model Hamiltonian allows us to successfully reproduce both the susceptibility and magnetisation data.     

Reaction products between sodium diphenyl -amine-4-sulfonate and hydrated LaCl3

This paper presents the reactions of synthesis between the ligand sodium diphenylamine-4-sulfonate and the lanthanum(III) chloride hydrated. The compounds (LaCl₃)₂·(C₁₂H₁₀NSO₃Na)₃·2(CH₃CH₂OH) (A) and (LaCl₃)·(C₁₂H₁₀NSO₃Na)·(CH₃CH₂OH)·12H₂O (B) were obtained using the solvents ethanol and methanol (synthesis A) and ethanol and water (synthesis B). The produced compounds and the ligand were characterized by thermogravimetric and differential thermogravimetric analysis, IR spectroscopy and elemental analysis of sodium, carbon, hydrogen, nitrogen, sulfur, chlorine and lanthanum, whereas the residues from thermal decomposition were investigated by X-ray diffractometry. This revised version was published online in August 2006 with corrections to the Cover Date.     

Methods for Elemental Analysis of Size-Resolved PM Samples Collected on Aluminium Foils: Results of an Intercomparison Exercise

Aluminium is the most common substrate in studies using impactors for the measurement of the number or the weight of size-segregated atmospheric particulate matter (PM), as its characteristics perfectly fit impactor requirements. However, its use is not recommended by manufacturers when one of the purposes of the study is the determination of the metal content in the sample. The aim of this work was to develop an efficient analytical procedure for the removal and acid digestion of PM samples collected on aluminium foils by a cascade impactor to perform the determination of metals. The possibility of performing the trace metal analysis of PM samples collected using aluminium foils is of great importance, as it allows the determination of an accurate size distribution and the elemental composition of the PM collected on each impactor stage. Two procedures were optimised by using different digestion and analysis techniques. Both procedures were then applied to the two halves of several Dekati low-pressure impactor (DLPI) samples, and the results were critically compared. The two procedures proved to be effective in the determination of extremely low concentrations of a large suite of analytes in different size fractions of PM emitted by a brake system.