On the Spectral Rigidity of Hopf Manifolds

We characterize Hopf manifolds of complex dimension 3 (resp. 2) in the class of compact locally conformal Kaehler manifold ( resp. Hermitian manifold ) by the spectrum of the Laplacian acting on functions.     

Higher order bad loci

Zero-schemes on smooth complex projective varieties, forcing all elements of ample and free linear systems to be reducible, are studied. Relationships among the minimal length of such zero-schemes, the positivity of the line bundle associated with the linear system, and the dimension of the variety are established. Bad linear spaces are also investigated.     

A calorimetric study of the different thermal behaviour of DNA in the isotropic and liquid-crystalline states

A difference between the thermal behaviour of the isotropic and liquid-crystalline state of sonicated DNA in aqueous salt solution containing poly(ethyleneglycol)(PEG) has been demonstrated. On cooling, a different degree of renaturation of thermally denaturated DNA is observed between samples which form the isotropic state and more concentrated samples which on cooling form the cholesteric state.     

Scattering of Magnetic Edge States

We consider a charged particle following the boundary of a two dimensional domain because a homogeneous magnetic field is applied. We develop the basic scattering theory for the corresponding quantum mechanical edge states. The scattering operator attains a limit for large magnetic fields which preserves Landau bands. We interpret the corresponding scattering phases in terms of classical trajectories. Communicated by Yosi Avron submitted 23/02/05, accepted 3/05/05     

Catalysis in aromatic nucleophilic substitution. Note II. Piperidino substitution reactions of some 2-l-3-nitrothiophenes and 2-l-5-nitrothiophenes in methanol and benzene

The rates of piperidino substitution of some 2-L-3-nitrothiophenes (I) and 2-L-5-nitrothiophenes (II) (L = Cl, Br, I, OC₆H₄NO₂-p, and SO₂Ph) have been measured in methanol and in benzene at various piperidine concentrations. The reactivity of compounds (I) is not affected by the piperidine concentration in both methanol and benzene, except for the case of L = I (Ic). Probably due to association effects, the reactivity of Ic in benzene decreases as the piperidine concentration is increased. The reactions of compounds II follow overall second order kinetics in methanol while in benzene a different behaviour is observed as a function of the nature of the leaving group. In fact, the piperidino substitutions of IIa-c (L = Cl, Br, I) are mildly accelerated at high piperidine concentrations (a moderate solvent effect); on the contrary the reactivity of IId and e shows a strong dependence on the piperidine concentration, pointing out a genuine base catalysis.     

DFT computational study of the mechanism of allyl halides carbonylation catalyzed by nickel tetracarbonyl

A theoretical investigation at the DFT(B3LYP) level on the carbonylation reaction of allyl bromide catalyzed by nickel tetra-carbonyl Ni(CO)(4) is discussed. The computational results show the following: (i) Three main steps characterize the catalytic cycle: (a) an oxidative addition step, (b) a carbonylation step, and (c) a reductive elimination step where the acyl product is obtained and the catalyst is regenerated. (ii) Both Ni(CO)(3) and Ni(CO)(4) complexes can behave as "active" catalytic species. (iii) The oxidative addition leads to the formation of either eta(3) or eta(1)-allyl nickel complexes, which are involved in a fast equilibrium. (iv) The carbonylation occurs much more easily on the eta(1) than on the eta(3) intermediates.     

On finite {1,2,3}-semiaffine planes

In this paper, we investigate {1,2,3}-semiaffine planes. All such planes of order n >51 shall be classified. It turns out that they are embeddable into projective planes of the same order n in the most natural way.Work supported by National Research Project on Strutture Geometriche Combinatoria, loro applicazioni of Italian M.P.I. and G.N.S.A.G.A. of C.N.R.     

Amphiphilic cyclodextrin carriers embedding porphyrins: charge and size modulation of colloidal stability in heterotopic aggregates

The interaction between the anionic 5,10,15,20-tetrakis(4-sulfonatophenyl)-21H,23H-porphyrin (TPPS) and cationic vesicles formed by heptakis(2-omega-amino-O-oligo(ethylene oxide)-6-hexylthio)-beta-cyclodextrin (SC6CDNH2) has been investigated in detail through a combination of elastic light scattering (ELS), quasi-elastic light scattering (QELS), zeta potential measurements, and time-resolved fluorescence anisotropy. ELS experiments provided the first structural characterization of these cationic vesicles both in the absence and in the presence of TPPS porphyrin, modeling the system as a spherical particle described by a single thin shell form factor. The structure of mixed hetero-aggregates is modulated by charge and size of the two components as function of different porphyrin/cyclodextrin (CD) molar ratios. At the limiting molar ratio studied, the absolute value of zeta potential (/zeta/ = 12.5 mV) seems to be a reference value for the formation of stable colloidal CD vesicular aggregates at thermodynamic equilibrium. New insights on the structure of these heterotopic colloids have been obtained by analysis of rotational correlation times at different molar ratios exploiting time-resolved fluorescence anisotropy experiments. At high porphyrin loads, the anisotropy decays behave as monoexponentials and the rotational correlation times (1-2 ns) together with the r(0) values close to zero suggest the presence of small amounts of TPPS embedded in a hydrophobic environment either in monomeric or in aggregated form. At the lower porphyrin/CD molar ratios, the anisotropy decays exhibit a double-exponential behavior showing a predominant component with a slow rotational correlation time (20-25 ns) and limiting anisotropy values of approximately 0.15. This component has been assigned to molecules that are more stabilized onto the CD vesicles, that is, porphyrins embedded into the oligo-ethylene "wall" of the CD vesicles. Scanning near-field optical microscopy of the samples evaporated on glass surfaces gave further insights on the morphology and optical properties of these systems, confirming the embedding of TPPS on the vesicles and evidencing the role of the solvent.     

Novel bifluorene based conjugated systems: synthesis and properties

A series of novel bifluorene based systems was synthesised by a convergent approach by means of a Suzuki cross-coupling between 7,7′-bis-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-9,9,9′,9′-tetraoctyl-2,2′-bifluorene and suitable aryl-bromides. All the oligomers have been characterized by ¹H, ¹³C NMR, FT-IR, UV-vis, PL spectroscopy and mass analyses. In particular, it has been demonstrated that the presence of strong electron donor (amines) or withdrawing (carboxylic esters) groups causes a bathochromic shift of the optical properties with respect to those of unsubstituted molecules. The effects of these functional groups on the HOMO-LUMO energy levels were investigated by cyclic voltammetry. Remarkably, the LUMO energy level of 7,7′-bis-[5′-carbodecaoxy-2,2′-bithiophen-5-yl]-9,9,9′,9′-tetraoctyl-2,2′-bifluorene (−3.07 eV) is strongly influenced by the presence of the ester functional group.