Copolymerization of Ethene and Carbon Monoxide with (Diphosphine)nickel Catalysts

This work presents the results of the ethene–CO copolymerization with in situ generated catalysts based on atropisomeric 1,4‐diphosphines and nickel(II). The influence of the reaction conditions and the NMR characterization of the copolymers are described.     

Underground waters quality in the province of Lecce (Apulia, Southern Italy)

This paper shows the results of underground waters last monitoring in the province of Lecce (Apulia, Southern Italy). We carried out the physical-chemical characterization of the aquifers and their classification in accordance to limit values sanctioned by Italian legislation in force, by European directives and by FAO, in order to define their quality and to establish their possible use for drinkable and irrigation purposes. The attention has been focused on salinity evaluation and underground waters contamination phenomena, due to sea-water intrusion and to the use of fertilizers. Salinity and nitrates concentrations are high in a few wells. Iron and manganese concentrations are very high for almost every sample and this is due to corrosion phenomena of artesian wells metallic structure. For a better interpretation of data, multivariate statistical analysis has been used, in order to obtain the correlation among analytical results, soils hydro-geological properties and anthropic conditions.     

Preliminary 1H NMR study on archaeological waterlogged wood

Magnetic Resonance Relaxation (MRR) and Magnetic Resonance Imaging (MRI) are powerful tools to obtain detailed information on the pore space structure that one is unlikely to obtain in other ways. These techniques are particularly suitable for Cultural Heritage materials, because they use water 1H nuclei as a probe. Interaction with water is one of the main causes of deterioration of materials. Porous structure in wood, for example, favours the penetration of water, which can carry polluting substances and promote mould growth. A particular case is waterlogged wood from underwater discoveries and moist sites; in fact, these finds are very fragile because of chemical, physical and biological decay from the long contact with the water. When wood artefacts are brought to the surface and directly dried in air, there is the collapse of the cellular structures, and wood loses its original form and dimensions and cannot be used for study and museum exhibits. In this work we have undertaken the study of some wood finds coming from Ercolano's harbour by MRR and MRI under different conditions, and we have obtained a characterization of pore space in wood and images of the spatial distribution of the confined water in the wood.     

113Cd NMR and fluorescence studies of multiple binding mechanisms of Cd(II) by the Suwannee River fulvic acid

The binding of Cd (II) by the fulvic acid from a Suwannee River (FA) was investigated at various pH values and reactants ratios by 113Cd NMR and fluorescence spectroscopy. The NMR results provided evidences that the FA-Cd interactions occur through a variety of binding modes and mechanisms. Different kinds of organically bound Cd-species were detected in the 1.8-10.8 pH range depending on the FA/Cd ratios. Labile complexes (amenable to Cd-aminoacidic and Cd-hydroxy interactions or outer-sphere complexes) were observed at low pH and FA/Cd levels while stronger interactions (of carboxylate-type or inner-sphere complexation) took place as the pH and/or the FA concentration were increased. At pH ca. 6 insoluble FA-Cd adducts were primarily produced but, at relatively large FA concentration, only soluble complexes, stable in the whole pH 1.8-10.8 range, were formed. A complementary analysis, by fluorescence spectroscopy, provided clear evidences of FA-Cd association/aggregation phenomena. While no noticeable effects occurred with soluble samples, the formation of insoluble adducts led to significant enhancements of the emission fluorescence spectra. Although other explanations could not be excluded, this result was accounted for by modifications of the optical properties of the ligand itself due to sedimentation of the heavier components. Fluorescence enhancement was also observed on samples before the effective precipitation and interpreted as spectroscopic evidence of the onset of aggregation phenomena.     

Exclusive transition state stabilization in the supramolecular catalysis of Diels-Alder reaction by a uranyl salophen complex

Whereas the parent uranyl salophen is catalytically inactive, its phenyl derivative effectively catalyses with turnover the reaction of benzoquinone with 1,3-cyclohexadiene, while showing no appreciable affinity towards reactants and product.