Preparation and physical characterization of forms II and III of paracetamol

The polymorphic forms II and III of paracetamol were obtained by melting the marketed form I. Under the melting and cooling conditions used, it was possible to obtain forms I, II and III. The recrystallization conditions and the physical properties of forms II and III were investigated by means of various techniques: thermomicroscopy, DSC analysis, infrared microspectrometry and X-ray powder diffraction at room temperature and as a function of temperature. Form III was found to be very unstable. However, its formation seems to be an important intermediate step in the preparation of form II.     

FT-EPR and HPLC study of the mechanism of 4-chlorophenol photolysis

The mechanism of 4-chlorophenol (4CP) photolysis was investigated with the aid of Fourier Transform Electron Paramagnetic Resonance (FT-EPR) and pulsed-laser photolysis combined with High Performance Liquid Chromatography (HPLC) detection-of stable (diamagnetic) products. With FT-EPR transient free radicals produced by pulsed-laser excitation of solutions of 4CP in alcohols could be identified. Time profiles of the FT-EPR spectra provided information on reaction kinetics and Chemically Induced Dynamic, Electron Polarization (CIDEP) effects. It was found that 4CP photolysis in alcohols leads to the simultaneous formation of the phenoxyl radical and radicals produced by hydrogen abstraction from the solvent. CIDEP patterns establish that these radicals are formed in a reaction sequence involving a triplet state precursor and radical pair intermediate. Results of earlier transient optical absorption measurements indicate that the triplet precursor must be the carbene 4-oxocyclohexa-2,5-dienylidene. This assignment is supported by the finding that photolysis of quinone diazide in a hydrogen-donating solvent gives the same free radical products as those obtained from 4CP. The formation of the phenoxyl radical intermediate accounts for the finding that photolysis of deoxygenated solutions of 4CP in alcohols gives phenol as stable diamagnetic product. By contrast, photolysis of aerated and deoxygenated aqueous solutions of 4CP produces benzoquinone and hydroquinone as primary products, respectively.     

FexNi100−x nanometric films deposited by laser ablation on SiO2/Si substrates

Fe_xNi_100−x nanometric films were deposited on SiO₂/Si substrates at room temperature using the pulsed laser deposition technique. The targets were Fe-Ni amorphous magnetic foils with composition Fe₅₀Ni₅₀, Fe₃₅Ni₆₅ and Fe₂₂Ni₇₈. Morphological and structural properties of the deposited films were investigated using scanning electron microscopy, Rutherford backscattering spectrometry, grazing incidence X-ray diffraction, and X-ray reflectivity. Electrical and magnetic characteristics of the films were investigated by using the four-point probe and the magneto-optic Kerr effect techniques, respectively. The film properties are strictly dependent on the Fe-Ni compositional ratio.     

A thorough study of the surface wax of apple fruits

The composition of the surface waxes of three apple ( Malus domestica L.) cultivars ("Florina", "Golden B" and "Ozark Gold") has been studied by means of spectroscopic and GC–MS analysis of the class-fractionated mixture of components. Odd n -alkanes, mainly C₂₇ and C₂₉ molecules, are prevalent in the saturated fraction. Small concentrations of alkenes were also found; the C_28:1 component is strongly (72%) in excess over the other 1-alkenes. Straight-chain esters (mainly of palmitic acid) of saturated primary alcohols (C₁₈–C₃₀) were also detected; whereas the acyl moiety is made up essentially of an even number of carbons, the alcohol counterpart does not exhibit this characteristic. Aldehydes are present (C₂₀–C₃₀) with the homologue patterns C₂₆–C₃₀ most strongly represented. Straight-chain free secondary alcohols characterize the waxes of "Florina" and "Ozark Gold"; the hydroxy function is located far from the extremity of the carbon framework. Outstanding is the presence of three alcohols with 29 carbon centres. These alcohols are accompanied by free straight-chain primary alcohols, mainly with even-numbered carbon chains in the range C₂₆–C₃₀. Free fatty acids are present; all of have a framework of even-numbered carbon chains mainly in the range C₁₆–C₂₀. C_18:1 (oleic acid) is well represented.     

1H-NMR,Ultraviolet and infrared spectra of some (Z)-α-(phenyl)-β-(2-furyl), -(2-pyrrolyl) and -(N-methyl-2-pyrrolyl)acrylonitriles

The ¹H-nmr data of some (Z)-α-(p-substituted-phenyl)-β-(2-furyl), -(2-pyrrolyl), and -(N-methyl-2-pyrrolyl)-acrylonitriles have been investigated to indicate the preferred conformation and to establish the conformational preferences of the β-heterocyclic ring. The ultraviolet spectra have been discussed in order to obtain information about the chromophores responsible for the absorption. The infrared spectra have been analyzed for the identification of the main absorption frequencies of cyano and ethylenic groups and to assign the characteristic absorption bands to specific normal vibrations of the heteroaromatic nuclei.     

Inter-annual variability in atmospheric input and partitioning of heavy metals in the Lagoon of Venice

Atmospheric bulk deposition of major and trace elements was measured at Venice from November 1995 to October 1997. Collection was carried out using polyethylene bulk passive samplers, samples being collected bi-weekly. In order to highlight the contribution of the atmosphere to water chemistry and particle budgets in the Lagoon of Venice, the geochemical composition (Si, Al, Ca, Mg, K, Na, Mn, Cr, Zn, Pb, Cd, Cu, As) of dissolved and insoluble bulk fractions was determined by AAS + ICP mass spectrometry. Great sample variability was found, with almost two orders of magnitude between maximum and minimum values for several metals. All fluxes in 1995/96 were 30% lower than in 1996/97, ranging from -3% (Ca) to -57% (Li), except for Zn, Cd and As. On the contrary, the solubility of all elements decreased during 1996/97. Partitioning between soluble and insoluble phases shows that Al, Cr, Fe and Si are mainly in the insoluble form, whereas for As, Ca, Cu, Mg, Na, Ni, K, Pb and Zn the dissolved fraction represents 50-90% of total input. The amount of particle load affects partitioning between dissolved and particulate, especially for Al and Pb. Seasonal variability was evident. The lowest pH values (approximately 5.2) were recorded in winter, causing an increase of solubility for all metals except for As, which showed the highest solubility in summer.     

Oxazinins from toxic mussels: isolation of a novel oxazinin and reassignment of the C-2 configuration of oxazinin-1 and -2 on the basis of synthetic models

The analysis of a batch of toxic mussels (Mytilus galloprovincialis) from the Northern Adriatic Sea led to the isolation of a novel oxazinin, oxazinin-4. Its structure including the relative stereochemistry has been elucidated through extensive NMR analysis. A synthetic route to oxazinins has been crucial in establishing the absolute stereochemistry of oxazinin-4 and for reassigning the absolute C-2 configuration of oxazinin-1 and -2 previously isolated from toxic shellfish and stereostructurally characterized.     

Synthesis and characterization of 4-hydroxy-3-phenylprolines

4-Hydroxy-3-phenylprolines were synthesized via 1-acetyl-2,2-diethoxycarbonyl-2,3-dihydro-3-phenyl-1H-pyrrole. Reversed phase hplc resulted in the isolation of the products which were characterized by ¹H and ¹³C nmr spectroscopy.     

Cohomology of groups with metacyclic Sylow -subgroups

We determine the cohomology algebras for all groups with a metacyclic Sylow -subgroup. The complete -local stable decomposition of the classifying space is also determined.