Aziridines—XVI: Etude des conformations privilegiees cycle aromatique-petit cycle dans les C-aryl aziridines N-non-substituees

The preferred conformation of phenyl-2 aziridine involves the phenyl ring nearly bisecting the plane of the small ring (maximum conjugation). As the steric hindrance due to substituents on the aromatic ring is more substantial, the aromatic ring moves towards a perpendical plane. Good agreement between experimental (IR and NMR) and theoretical studies of the syn-anti configurational equilibrium of NH in these compounds is demonstrated. The analysis of the total electronic populations clarifies an understanding of the variation of the charge transfer small ring?aromatic cycle as a function of the aromatic nucleus.     

Soliton dynamics in alternating trans-polyacetylene and in stacked systems

The influence of substitutional disorder, of random forces and of energy dissipation on solitons in alternating trans-polyacetylene using the Su-Schrieffer-Heeger Hamiltonian is discussed. Double ionization in polyene chains was also investigated. Further soliton dynamics within a full Pariser-Parr-Pople Hamiltonian for trans-polyacetylene are presented. The presence of conformational solitons in stacked systems is shown numerically in a polyformamide model system. Possible relations to DNA and carcinogenesis are briefly reviewed.     

Stereoselectivity and chiral recognition in copper(I) olefin complexes with a chiral diamine

Trigonal copper(I) complexes of the chiral bidentate ligand (1S,2S)-N,N'-Bis-(mesitylmethyl)-1,2-diphenyl-1,2-ethanediamine ((S,S)-1) have been prepared with hydrocarbon olefins, as well as with allylic alcohols and ethers. The stereochemistry of the complexes has been investigated by 1H NMR spectroscopy and by combined quantum mechanics and molecular mechanics (QM/MM) computational methods. The coordinated chiral nitrogen atoms can display equal (R, R) or opposite (R, S) configuration, the latter being disfavored if steric hindrance is present above and below the coordination plane. Although the complexes exist as rapidly equilibrated mixtures of stereoisomers, one of these is often dominant, and prochiral olefins are coordinated with high enantioface selection. In addition, the [(S,S)-1]-Cu+ fragment selectively recognizes the R enantiomer of secondary allylic alcohols and ethers, as confirmed by the X-ray crystal structure analysis of the adduct with (R)-1-buten-3-ol. The reasons for the observed selectivities have been elucidated, and lead to some implications which are consistent with the enantioselection observed in catalytic cyclopropanation reactions promoted by copper complexes of the same ligand.     

Double resonance observation of the (2ν3, E) state in methane

By using the double resonance technique we have observed the infrared inactive (2ν₃, E) level in methane. The experimental value of the vibrational energy (6043.8 cm^?1) is in good agreement with recent calculations based on the “local mode” model.     

Differentiation among dairy products by combination of fast field cycling NMR relaxometry data and chemometrics

A set of commercial milk and Sicilian cheeses was analysed by a combination of fast field cycling (FFC) nuclear magnetic resonance (NMR) relaxometry and chemometrics. The NMR dispersion (NMRD) curves were successfully analysed with a mathematical model applied on Parmigiano–Reggiano (PR) cheese. Regression parameters were led back to the molecular components of cheeses (water trapped in casein micelles, proteins and fats) and milk samples (water belonging to hydration shells around dispersed colloidal particles of different sizes and bulk water). The application of chemometric analysis on relaxometric data enabled differentiating milk from cheeses and revealing differences within the two sample groups of either cheeses or milk samples. Marked differences among cheeses were evidenced by statistical analysis of the sole quadrupolar peaks parameters, suggesting that these contain information on the nature of the milk used during cheese production. Hence, combination of FFC NMR and chemometrics represents a powerful tool to investigate alterations in dairy products.     

Cross-linked natural IntegroPectin films from citrus biowaste with intrinsic antimicrobial activity

Cellulose - Pectin recovered via hydrodynamic cavitation (IntegroPectin) from lemon and grapefruit agri-food waste intrinsically containing antimicrobial bioactive substances (flavonoids, phenolic...     

Studies on the V2O5?TiO2 system, V. Equilibrium pressures

The oxygen equilibrium pressures from pure V₂O₅ and co-precipitated V₂O₅–TiO₂ system were measured in the range of 200–450 °C. The behavior of the equilibrium pressure with changes of temperature of the samples with and without TiO₂ is attributed to Ti⁴⁺ interaction with the V₂O₅ lattice.

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V₂O₅ - V₂O₅–TiO₂ 200–450°C. TiO₂ Ti⁺⁴ V₂O₅.

     

Amperometric Glucose Determination by Means of Glucose Oxidase Immobilized on a Cellulose Acetate Film: Dependence on the Immobilization Procedures

Glucose microelectrodes were prepared by immobilizing glucose oxidase onto a cellulose acetate film coating a platinum wire. Hexamethylenediamine (HMDA) and Glutaraldehyde (GA) were employed as spacer and coupling agent, respectively. Sensitivities and linear response ranges were studied as a function of the relative amounts of HMDA and GA. The best sensitivity was found when HMDA and GA were 5% and 2.5% in aqueous solutions, respectively. Taking as a reference the functioning of this biosensor, the roles of HMDA and GA percentages appear to be opposed when the extension of the linear response range is considered. Indeed, an increase of one unit in HMDA percentage (from 5 to 6 %) induces an increase in the extension of the linear response range equal to that obtained with a decrease of one unit of GA percentage (from 2.5 to 1.5%).     

Surface nitridation by multipulse excimer laser irradiation

A review is presented of the results obtained on the formation of nitride surface layers on semiconductor (Si) and metal (Ti) samples by multipulse (up to 2500) XeCl excimer laser (λ=308 nm) irradiation in N₂ and NH₃ atmosphere through a collaboration of Italian, Czechoslovak and Romanian laboratories. Different diagnostic techniques (optical and electron microscopy, Rutherford backscattering spectroscopy, nuclear reaction analysis, Auger and x-ray photoelectron spectroscopy) were used to positively identify the formed compounds. Silicon nitride formation was obtained only when laser irradiation was performed in ammonia atmosphere. In contrast, when titanium samples were irradiated the nitridation process resulted very efficient in both atmospheres. The characteristics of laser synthesized nitride layers are illustrated and discussed as a function of the kind of irradiated materials, the number of subsequent laser pulses and the nature of the ambient gas.     

Vector magnetisation measurements on thermally evaporated CoCr multilayers and solid solutions for spintronic applications

Structure, morphology and magnetic properties of thermally evaporated Co/Cr multilayers and of the solid solution obtained by isothermal treatment of the layered samples have been studied to evaluate their potential application as high-coercivity materials for hard spin injectors in spintronic devices such as magnetic tunneling junctions. The thermal treatment was performed in a partial pressure of inert gas to allow interdiffusion of Cr and Co. Structure and composition of the materials, as well as the effects of the annealing treatment, have been investigated by field emission scanning electron microscopy and energy-dispersive X-ray analysis. The magnetic configuration of these films was investigated by magnetic force microscopy. Simultaneous measurements of two mutually perpendicular magnetisation components were performed by means of a vector vibrating sample magnetometer, and showed that the in-plane coercivity can be increased by proper thermal treatment from less than 10 Oe to about 240 Oe. However, annealing may result in a loss of compositional and morphologic homogeneity of the films.