Mass spectrometric studies of 2-aryl-5-acetylthiazole derivatives

Electron ionisation mass spectrometry was usefully used to characterize structurally 2-aryl-5-acetylthiazole derivatives in the gas phase. The compounds show characteristic fragmentation pathways depending on the chemical nature of the substituent at position 2, consisting mainly in the cleavage of both the 1,2- and 3,4-bonds of the thiazole ring. Liquid secondary ion mass spectrometry was applied to study the effects of protonation on the gas-phase unimolecular reactions of this class of compound. Tandem mass spectrometric experiments, carried out on molecular and protonated molecular ions, and also on fragment ions produced in the source, allowed the elucidation of gas-phase decompositions of low-internal energy ions.     

meso-Me2Si(1-indenyl)2ZrCl2/methylalumoxane catalyzed polymerization of the ethylene to ethyl-branched polyethylene

The meso ansa zirconocene with dimethylsilyl bridge, activated by methylalumoxane, catalyses the ethylene polymerization, producing ethyl-branched polyethylene. With respect to the polymers obtained with the previously investigated meso zirconocenes, we have found higher branching amount and lower molecular weight. The rapid β-H transfer from the growing chain to the coordinated monomer could account for both these features of the polymer. The investigation on the structural parameters of the complex, through X-ray diffraction analysis, and on the electrophilicity of the cationic center, through NMR experiments, suggests, as a possible rationalization of this behavior, the obstruction in the inward site.     

A computational tool for the prediction of crystalline phases obtained from controlled crystallization of glasses

An automatic tool (named CLUSTER) for the prediction of the most probable crystal phases that can separate from glasses has been developed. The program analyzes the output of molecular dynamics simulations of glasses or glass ceramics, systematically sampling the ratios of the ions in different portions of the simulation box and comparing them to the stoichiometric ratio of compositionally equivalent crystalline phases retrieved from a crystal structure database. The efficacy of the similarity index elaborated has been judged by comparing the results obtained with the crystal phases identified by XRD analysis after thermal treatment in a series of multicomponent potential bioactive glasses and glass ceramics for which the advantages of rational-designed erosion-controlled release is straightforward.     

Coordination behavior toward copper(II) and zinc(II) ions of three ligands joining 3-hydroxy-2-pyridinone and polyaza fragments

The synthesis and characterization of new polydentate ligand 2-(N),2'-(N')-bis[2-(3-hydroxy-2-oxo-2H-pyridin-1-yl)acetamido]-1(N'),2(N),2'(N')-trimethyl-2,2'-diaminodiethylamine (L3) is reported. The coordination properties of L3 and of two analogous macrocyclic ligands (L1 and L2) toward Cu(II) and Zn(II) metal ions are reported. All three ligands show the 3-hydroxy-2(1H)-pyridinone (HPO) groups attached as sidearms to a polyaza fragment, which is a macrocyclic framework in the case of L1 and L2 while it is an open chain in the case of L3. The role of the polyaza fragments in preorganizing the two sidearms was investigated. The basicity of L3 and the binding properties of L1-L3 were determined by means of potentiometric measurements in aqueous solution (298.1 +/- 0.1 K, I = 0.15 mol dm(-3)). UV-vis spectra as well 1H and 13C NMR experiments were used to understand the role of the HPO and of the polyaza fragments in the stabilization of the cations. While L1 forms stable mono- and dinuclear complexes, L2 and L3 can form only mononuclear species with each of the metal ions investigated. In the main mononuclear species of L2 and L3, the two HPO moieties stabilize the M(II) in a square planar geometry due to the two oxygen atoms of each HPO. The coordination sphere of the metal is completed by adding a secondary ligand such as water molecules in the case of Cu(II) systems or OH- in the Zn(II) systems. These results are confirmed by the crystal structures of the [CuH(-1)L2]+ and [CuH(-1)L3]+ species reported herein. Two conformations of L1 can be hypothesized in the formation of the dinuclear species, as suggested by NMR experiments on the [ZnH(-2)L1] species, which shows two conformers slowly interchanging on the NMR time scale, one of which was found to be more insoluble.     

Synthesis and characterization of a new benzofulvene polymer showing a thermoreversible polymerization behavior

A new polymer based on a functionalized benzofulvene moiety has been synthesized by spontaneous polymerization of the monomer in the solid state. This polymer shows a very high molar mass, high solubility in the most common organic solvents, and thermoreversible polymerization properties. An interesting application in synthesis is reported.     

Rearrangement of N-Allyl-α,α-dichloroamides, β- or γ- Functionalized,to Substituted Analogues of the γ-Aminobutyric Acid (GABA)

The rearrangement of γ-chlm, β-hydroxy or β-vmyl N-allyl-N-benzyl-α,α-dichlorocarboxyamides to γ-aminobutynic acid analogues is efficiently promoted by CuCI\N,N,N′,N′-tetramethylethylendiamine. With the β-vinyl functionalization a tandem radical-radical reaction, yieldmg 3-aza-2-oxo-bicyclo[3,3,0]actatre adducts, is also observed.     

The influence of normal stress anisotropy in predicting scalar dispersion with the v–f model

A numerical study of scalar dispersion is presented to investigate the effectiveness of pairing the v²–f turbulence model with algebraic models for the scalar flux. This approach is contrasted with utilizing a full Second Moment Closure (SMC) as the flow field input to the scalar model. Predictions of scalar transport in a turbulent channel and over a wavy wall are compared to available DNS databases. The latter case includes a scalar release from a point source and therefore detailed comparisons of the three-component turbulent scalar flux are reported. It is found that the transported variable v², representing the near wall turbulent velocity fluctuation scale, can be used to increase the level of normal stress anisotropy provided to algebraic scalar models and thereby improve mean scalar prediction over that of the Standard Gradient Diffusion Hypothesis (SGDH). Improvement is most significant in the near wall region. Three specifications of the normal stresses, derived from v², are considered to provide the link from the v²–f model to the algebraic flux models used to close the scalar transport equation. Barycentric maps are used to examine the state of turbulence anisotropy in each case. As the anisotropy in the normal stress specification becomes more accurate, improvements are realized in the prediction of the spanwise flux as well as the mean concentration.     

Geometric Currents in Piezoelectricity

As a simple model for piezoelectricity we consider a gas of infinitely many non-interacting electrons subject to a slowly time-dependent periodic potential. We show that in the adiabatic limit the macroscopic current is determined by the geometry of the Bloch bundle. As a consequence we obtain the King-Smith and Vanderbilt formula up to errors smaller than any power of the adiabatic parameter.     

Symmetry and Localization for Magnetic Schrödinger Operators: Landau Levels,Gabor Frames and All That

We investigate the relation between broken time-reversal symmetry and localization of the electronic states, in the explicitly tractable case of the Landau model. We first review, for the reader’s convenience, the symmetries of the Landau Hamiltonian and the relation of the latter with the Segal-Bargmann representation of Quantum Mechanics. We then study the localization properties of the Landau eigenstates by applying an abstract version of the Balian-Low Theorem to the operators corresponding to the coordinates of the centre of the cyclotron orbit in the classical theory. Our proof of the Balian-Low Theorem, although based on Battle’s main argument, has the advantage of being representation-independent.