Determination of hydroxycarbamates in aqueous matrices by direct derivatization and GC-MS analysis in chemical ionization mode

A rapid and effective procedure, developed for the determination of polar compounds in water, has been applied to hydroxycarbamates. In few minutes, it is possible to perform a catalyzed derivatization of such compounds directly in the aqueous medium, using n-hexyl chloroformate. Extraction with n-hexane and injection into a benchtop GC-MS system are the only two further steps to complete the analysis. Chemical ionization proved to be more effective than electron impact to produce valuable mass spectra in terms of selectivity and sensitivity. Linear quantitative responses were demonstrated over a two-order-of-magnitude range. The minimum detectable concentration was 3 ppb for acetohydroxamic acid and 10 ppb for hydroxyurethane, obtained from Po river water samples spiked with the two hydroxycarbamate standards.     

Enthalpic determinations of aliphatic ester-solvent systems with correlations

Calorimetric measurements were carried out on ester-solvent systems where the esters were H(CH₂)_xCOO(CH₂)_yH, with x and y varying from 1 to 5, and the solvents were n-hexane and 1,2-dichloroethane. Calculation of the enthalpies of cavity formation enabled the enthalpies of interaction to be determined. Both enthalpies correlated with number of carbon atoms N, equal to x+y in the esters, giving for 1,2-dichloroethane

Wavy graphene sheets from electrochemical sewing of corannulene

The presence of non-hexagonal rings in the honeycomb carbon arrangement of graphene produces rippled graphene layers with valuable chemical and physical properties. In principle, a bottom-up approach to introducing distortion from planarity of a graphene sheet can be achieved by careful insertion of curved polyaromatic hydrocarbons during the growth of the lattice. Corannulene, the archetype of such non-planar polyaromatic hydrocarbons, can act as an ideal wrinkling motif in 2D carbon nanostructures. Herein we report an electrochemical bottom-up method to obtain egg-box shaped nanographene structures through a polycondensation of corannulene that produces a new conducting layered material. Characterization of this new polymeric material by electrochemistry, spectroscopy, electron microscopy (SEM and TEM), scanning probe microscopy, and laser desorption-ionization time of flight mass spectrometry provides strong evidence that the anodic polymerization of corannulene, combined with electrochemically induced oxidative cyclodehydrogenations (Scholl reactions), leads to polycorannulene with a wavy graphene-like structure.

A bottom-up synthesis of wavy graphene structures obtained through an anodic polymerization process, combined with an electrochemically triggered oxidative cyclodehydrogenation, of the bowl-shaped polyaromatic hydrocarbon corannulene.     

The Dold-Lashof-Fuchs construction revisited

Sia dato uno spazio topologicoE con azione di un monoide topologicoH e siaE→B una funzione continue che, su ogni apertoU di una partizione dell'unità diB, sia, a meno di omotopia, la proiezioneU×H→U (ovvero una fibrazione numerabile). Un classico risultato di A. Dold e R. Lashof (1959) permette di costruire, a partire daE→B, una funzione continuaE _∞→B_∞, conE _∞ debolmente contraibile e munito di azione diH: laH-fibrazione universale associata daH. Tale funzione, in generale, non è purtroppo numerabile e quindi non si presta alla classificazione delleH-fibrazioni numerabili. Successivamente (1971), M. Fuchs ha trovato un modo di modificare la costruzione di Dold-Lashof per recuperare la numerabilità. La costruzione di Dold-Lashof-Fuchs è, da allora, uno dei principali strumenti nella teoria degli spazi classificanti di monoidi topologici, anche se vi è un uso di topologie alquanto complesse e quindi poco maneggevoli. In questo lavoro ci proponiamo di mostrare come, lavorando nella categoria conveniente deik-spazi, sia possibile descrivere la costruzione di Dold-Lashof-Fuchs in modo estremamente semplificato ed adattarla anche alla classificazione delleF-fibrazioni numerabili.

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Conferenza tenuta da R. Piccinini il 15 maggio 1995     

A goldstone mode in the Kawasaki-Ising model

The hydrodynamic regime of superfluids is dominated by a Goldstone mode corresponding to a spontaneously brokenU(1) symmetry. In this article we map the Kawasaki-Ising model for a classical lattice gas into a quantum model for a superfluid and establish a connection between the normal density fluctuations of the first and the Goldstone mode of the second. The fact that the quantum model we obtain describes a superfluid derives from an inequality by Penrose and Onsager which gives a lower bound to the Bose-Einstein condensate density. Mathematically, the Goldstone mode can be described by means of a quantum extension of the local algebra of the Ising model. The classification of its irreducible representations requires an additionalU(1) phase factor and the correspondingU(1) gauge symmetry is spontaneously broken for all finite values of the temperature and of the density.     

Multivoice Littlewood-Paley-Meyer wavelets and diagonal dominated pseudodifferential operators

Given a pseudodifferential operator (p) satisfying certain growth and smoothness conditions in momentum space, we construct a wavelet basis ofL ²( ^d ) in which the corresponding matrix is diagonal dominated with arbitrarily small prefactor.     

The adiabatic approximation for quantum spin systems with a spectral gap

Summary We estimate the accuracy of the adiabatic approximation in predicting the time evolution of local observables for an XY quantum magnet with a slowly variable external magnetic field. The system evolves according to the natural Hamiltonian dynamics and the spectral gap produced by the magnetic field is assumed to be large with respect to the term inducing quantum fluctutions. The proof is based on a finite order truncation of a time dependent cluster expansion in inverse powers of the time scale . In the analytic case, we show that the accuracy of this truncated expansion is of order for any >1. If the time dependent perturbation is suddenly switched on at time zero and switched off at time , the accuracy of the adiabatic approximation is proven to be of orderO( ^–1.     

Determination of coplanar and non-coplanar polychlorinated biphenyls in human serum by gas chromatography with mass spectrometric detection: electron impact or electron-capture negative ionization?

A time- and cost-saving method for the congener-specific analysis of polychlorinated biphenyls (PCBs) in human serum has been developed and validated. After two fast extraction and clean-up steps, analyses were performed using gas chromatography coupled with mass spectrometry with single ion monitoring (GC/SIM-MS), either in electron impact (EI) or electron-capture negative ionization (ECNI) mode. For the determination of dioxin-like congeners, an improvement in EI-MS sensitivity is desirable and use of NI is thus preferred. The procedure was validated for 12 dioxin-like congeners by analyzing spiked samples on three different days and using (13)C(12)-labelled analogues as internal standards. When using an NCI source, the limit of quantification was assessed at 0.01 microg/L, except for PCBs #77 and #81, which cannot be reliably detected below 0.05 microg/L. For the lower chlorinated non-dioxin-like congeners, NI offers less selectivity because of limited fragmentation. Electron impact ionization and electron-capture negative ionization mode can therefore be considered to be complementary for the determination of PCB congeners in the general population.     

The First VOPO4·2H2O Intercalation Compound Synthesized through a Solid-State Reaction at Room Temperature

This communication reports the first intercalation into VOPO₄·2H₂O performed through a solid-state reaction at room temperature. Ethyleneurea, EU (2-imidazolidone) was intercalated into the oxovanadium phosphate by grinding in a mortar stoichiometric amounts of both reagents at room temperature for 30 min. C, H and N elemental analyses of the obtained intercalation compound gave the formula VOPO₄·(EU)·H₂O. The profile of the absorption bands due to the VOPO₄ lattice vibration around 1000 cm⁻¹ was retained after reaction, providing evidence that an intercalation compound and not merely a salt of V-P-O species was produced. For α-VOPO₄·2H₂O, the interlayer distance is 0.75 nm, whereas for the EU inter-calation compound it is 0.95 nm. The obtained SEM micrographs show that the microstructure of VOPO₄·2H₂O is changed after reaction, with a total exfoliation of the oxovanadium matrix.     

Electronic and Steric Influence of Axial and Equatorial Ligands in Vitamin B12 Model Complexes Derived from Cobaloxime: Electrochemical and 59Co-NMR Studies

In four series of strictly related organocobalt complexes, derived from cobaloximes by replacement of the O…H…O with O…-BF₂…O and/or (CH₂)₃ groups, the trends of ⁵⁹Co-NMR shielding and electrochemical data are discussed. A largely parallel behaviour of the plots of E_1/2(I) values for the first Co(III)/Co(II) electron transfer vs. the ₅₉Co chemical shifts reflects the similar sensitivity of the two parameters to a change in electron affinity of the central metal ion due to a variation of the organic group R. E_1/2(II) values for the second Co(II)/CO(I) electron transfer are less sensitive to the change of R, but the trend of the plot vs. δ(₅₉Co) is still parallel in the four series. Consistent deviations from a roughly linear dependence of E_1/2(I) on pK_a of the hydrocarbon acid corresponding to R, on Taft constant s?_* and on ⁵⁹Co shielding are noticed for the isopropyl derivatives and attributed to a steric effect. This was confirmed in a series of R? Co(DMG)pyridine complexes in which ⁵⁹Co shielding decreases steadily with increasing steric parameter E_s (Taft) of the alkyl group. There is experimental evidence from X-ray data that δ(⁵⁹Co) decreases with an increase of the Co? C bond length, illustrating steric hindrance in alkyl coordination to be responsible for the decreased shielding of the ⁵⁹Co nucleus. The relative displacements of the graphic displays for the different series reflect the effect of changes in electron affinity of the redox center, due to the equatorial ligand, which, in turn, is caused by variations in the electron-withdrawing power due to the introduction of the BF₂ group and by the change from ?2 to ?1 valence of the (CH₂)₃-capped ligands.