Effect of ring size on the tautomerization and ionization reaction of cyclic 2-nitroalkanones: an experimental and theoretical study

The keto-enol tautomerism of some cyclic 2-nitroalkanones was studied in cyclohexane. Keto-enol equilibrium constants, K(T), at 25 °C were obtained from (1)H NMR spectra. The relative enol content for the investigated ketones as a function of ring size decreases in the order 6 > 7 > 11 > 12 > 15. This trend apparently is different from that observed in water. Density functional theory (DFT) calculations have been performed to rationalize the effects of ring size and of the solvent on tautomerism. The acidity constants, K(a)(KH), for the different keto tautomers were measured spectrophotometrically at 25 °C in buffered aqueous solutions. No simple correlations between K(a)(KH) and ring size was observed, and this is in agreement with a DFT analysis performed on the same compounds.     

Determination of the polarities of some ionic liquids using 2-nitrocyclohexanone as the probe

Solute-solvent interactions on the keto-enol tautomerism of 2-nitrocyclohexanone in several organic solvents and room-temperature ionic liquids (RTILs) have been analyzed in terms of multiparameter equations. Permittivity and cohesive pressure values of the RTILs, unavailable by direct measurements, have been derived.     

1,3-Dipolar cycloaddition reactions. Regioselective synthesis of heterocycles and theoretical studies

We report a 1,3-dipolar cycloaddition reaction between a oxazolium 5-oxide derivative with chloroacrylonitrile or ethyl propiolate as dipolarophiles, in order to obtain substituted pyrrolizidines. Experimentally we found that the reaction is regiospecific with chloroacrylonitrile and regioselective with ethyl propiolate. The secondary attractive orbital interactions from the Frontier Molecular Orbital Theory, the differences in stability of the possible biradical intermediaries postulated for the reaction and some hindrance effects, explain the regioselectivity observed experimentally.     

Conformational studies by dynamic NMR. 89. Stereomutation and cryogenic enantioseparation of conformational antipodes of hindered aryl oximes

Aryl benzyl oximes having the configuration Z give rise to stereolabile atropisomers when a halogen atom is present in the ortho position of the aryl moiety, as a consequence of the restricted aryl-CN bond rotation. By means of dynamic (1)H NMR spectroscopy it has been possible to determine the corresponding rotation barrier, hence the lifetime of the atropisomers that, in the case of the iodine derivative, was found sufficiently long as to allow a physical separation to be achieved on an appropriately cooled enantioselective HPLC column. Comparison of the barriers determined by dynamic NMR and dynamic HPLC proved the equivalence of the two techniques. When the iodine atom was substituted by an alpha-naphthyl group, two dynamic processes were observed. That with the lower barrier could be determined by NMR and that with the higher barrier by HPLC, thus outlining the complementarity of these two techniques.     

Comparison of solid-phase extraction and micro-solid-phase extraction for liquid chromatography/mass spectrometry analysis of pesticides in water samples

Our recent on-line solid-phase extraction (SPE) device for micro-liquid chromatography, known as micro-solid-phase extraction (microSPE), was compared with traditional SPE for the analysis, from aqueous samples, of 4 pesticides belonging to different classes. Two different kinds of adsorbents, C18 and graphitized carbon black, were tested. A 2-stage ion trap mass spectrometer, equipped with homemade microflow electrospray ion (ESI) source, was used. Detection limits with a signal-to-noise ratio of 3:1 for both extraction methods were in the range of 0.1 microg/L for all compounds. However, better recoveries were obtained when microSPE traps were used.     

Photo-SRN1 reactions of phenyl telluride anion with haloarenes

Phenyl telluride anion was prepared in liquid ammonia by reaction of dipheyyl ditelluride with two equivalents of sodium metal under nitrogen. This anion reacts with haloarenes under irradiation to form aryl phenyl tellurides, probably by the photo-S_RN1 mechanism of aromatic substitution.     

Discrepancies between linear viscoelastic measurements and double-reptation predictions for commercial polystyrene samples

We have found discrepancies between the predictions of two double-reptation models and the corresponding linear viscoelasticity measurements for commercial, polydisperse polystyrene samples with weight-average molecular weights ranging from 140 to 300kg/mol. The accuracy of the experimental data has been confirmed by conducting viscoelasticity measurements in different laboratories using different types of rheometers and by verifying that small distortions in chromatographic measurements cannot account for the discrepancies seen in the viscoelastic response. In addition, we show that the discrepancies between predictions and measurements are systematic, suggesting that gaps in the theory are responsible for the mismatch. Is it concluded that commercial polystyrene resins may pose additional challenges for rheological modeling because of their relatively high polydispersity and low degree of entanglement. The experimental data given here can be used to validate future modeling efforts.     

Solitons in a channel emerging from a three-dimensional initial wave

Summary An implicit, three-time level, finite-difference scheme is presented which solves the initial-boundary-value problem for a regularized Kadomtsev-Petviashvili equation, modelling the evolution of a variety of wave systems for which weak dispersive, nonlinear and three-dimensional effects are taken into account. Linear and nonlinear tests are performed to test the scheme and the numerical results are found to compare accurately with known theoretical solutions. The evolution of a localized weakly three-dimensional initial condition in a channel is then studied. In all cases the numerical experiments show that the wave tends to a two-dimensional state: for initial waves with positive net volume two-dimensional solitons rapidly emerge. This behaviour agrees with laboratory experiments performed by different authors. Moreover, the radiation yields three-dimensional patterns similar to Genus 2, solutions of the KP equation.

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Riassunto Si presenta uno schema alle differenze finite implicito e a tre livelli temporali per una versione regolarizzata dell'equazione Kadomtsev-Petviashvili, descrivente la dinamica di una vasta classe di sistemi d'onda per i quali si hanno deboli effetti dispersivi, non lineari e tridimensionali. Una serie di test lineari e non lineari dà risultati numerici coincidenti con le corrispondenti soluzioni teoriche. Si analizza quindi l'evoluzione in un canale rettangolare di condizioni iniziali tridimensionali localizzate. In tutti i casi si osserva un processo di aggiustamento bidimensionale. Solitoni bidimensionali emergono rapidamente da onde iniziali positive. Ciò concorda con esperimenti di laboratorio. Inoltre il campo di radiazione si presenta sotto forma di onde tridimensionali simili alle solizioni di Genus 2 dell'equazione KP.

     

Comparison of chemical and physical properties of carbon blacks for sampling and analysis of environmental pollutants

Summary Some of the most commonly employed carbon blacks (Carbograph 1,2,4,5 from Lara and Carbopack X form Supelco), were evaluated by the BET surface characterization method for pore size distribution, porosity and specific surface. This information is often incomplete as furnished by manufacturers and is needed for a deeper understanding of carbon adsorption properties in chromatography. The data on surface characterization were obtained before and after graphitisation treatment (except for Carbopack X which could not be obtained in non-graphitized form). The nature of the active sites present on these carbons was investigated by BET analysis, atomic absorption and FT-IR. Dedicated to the memory of F. Bruner and G. Crescentini, pioneers in the study of graphitized carbon blacks for the sampling and analysis of environmental pollutants [1–4].     

Evaluation of a new graphitized carbon black employed in sampling volatile organic compounds

A new adsorbent, high-surface-area graphitized carbon black (HSGCB), with a surface area of 560 m²/g, superior to that of commonly traded graphitized carbons, was studied. The evaluation was performed in terms of breakthrough volumes and thermal desorption recoveries of substances representative of the main classes of organic compounds. HSGCB was found to be an interesting alternative to activated charcoal for volatile compounds in that it can be used in thermal desorption.