Cyclic carbonate formation from carbon dioxide and oxiranes in tetrabutylammonium halides as solvents and catalysts

[reaction: see text] Epoxides dissolved in molten tetralkylammonium salts bearing halides as counterions are converted into cyclic carbonates under atmospheric pressure of carbon dioxide. The reaction rate depends on the nucleophilicity of the halide ion as well as the structure of the cation.     

Photoinduced electron transfer in a triad that can be assembled/disassembled by two different external inputs. Toward molecular-level electrical extension cables

We have designed, synthesized, and investigated a self-assembling supramolecular system which mimics, at a molecular level, the function performed by a macroscopic electrical extension cable. The system is made up of three components, 12+, 2-H3+, and 3. Component 12+ consists of two moieties: a [Ru(bpy)3]2+ unit, which plays the role of an electron donor under light excitation, and a DB24C8 crown ether, which fulfills the function of a socket. The wire-type component 2-H3+ is also composed of two moieties, a secondary dialkylammonium-ion center and a bipyridinium unit, which thread into the DB24C8 crown-ether socket of 12+ and the 1/5DN38C10 crown-ether socket 3, respectively. The photochemical, photophysical, and electrochemical properties of the three separated components, of the 12+ superset 2-H3+ and 2-H3+ subset 3 dyads, and of the 12+ superset 2-H3+ subset 3 triad have been investigated in CH2Cl2 solution containing 2% MeCN. Reversible connection/disconnection of the two plug/socket systems can be controlled independently by acid/base and redox stimulation. The behavior of the various different dyads and triad has been monitored by light absorption and emission spectroscopies, as well as by electrochemical techniques. In the fully connected 12+ superset 2-H3+ subset 3 triad, light excitation of the [Ru(bpy)3]2+ unit of component 12+ is followed by electron transfer (k = 2.8 x 108 s-1) to the bipyridinium unit of component 2-H3+, which is plugged into component 3. Possible schemes to obtain improved molecular-level electrical extension cables are discussed.     

Theoretical evaluation of zirconia and hafnia as gate oxides for si microelectronics

Parameters determining the performance of the crystalline oxides zirconia (ZrO2) and hafnia (HfO2) as gate insulators in nanometric Si electronics are estimated via ab initio calculations of the energetics, dielectric properties, and band alignment of bulk and thin-film oxides on Si (001). With their large dielectric constants, stable and low-formation-energy interfaces, large valence offsets, and reasonable (though not optimal) conduction offsets (electron injection barriers), zirconia and hafnia appear to have considerable potential as gate oxides for Si electronics.     

Peroxynitrite decomposition catalyst prevents apoptotic cell death in a human astrocytoma cell line incubated with supernatants of HIV-infected macrophages

Background  

Oxidative stress has shown to contribute in the mechanisms underlying apoptotic cell death occuring in AIDS-dementia complex. Here we investigated the role of peroxynitrite in apoptosis occurring in astroglial cells incubated with supernatants of HIV-infected human primary macrophages (M/M).     

Computing automorphisms of abelian number fields

Let be an abelian number field of degree . Most algorithms for computing the lattice of subfields of require the computation of all the conjugates of . This is usually achieved by factoring the minimal polynomial of over . In practice, the existing algorithms for factoring polynomials over algebraic number fields can handle only problems of moderate size. In this paper we describe a fast probabilistic algorithm for computing the conjugates of , which is based on -adic techniques. Given and a rational prime which does not divide the discriminant of , the algorithm computes the Frobenius automorphism of in time polynomial in the size of and in the size of . By repeatedly applying the algorithm to randomly chosen primes it is possible to compute all the conjugates of .

     

Generation of analytic semigroups in theL p topology by elliptic operators inR n

Strongly elliptic differential operators with (possibly) unbounded lower order coefficients are shown to generate analytic semigroups of linear operators onL ^p(R ⁿ ), 1≦p≦∞. An explicit characterization of the domain is given for 1<p<∞. An application to parabolic problems is also included. This work has been partially supported by the Research Funds of the Ministero della Pubblica Istruzione. The authors are members of GNAFA (Consiglio Nazionale delle Ricerche).     

Numerical simulation of free-surface thermally influenced flows for nonhomogeneous fluids

A finite-difference technique is presented to simulate the behavior of natural water bodies under the influence of pollutants and temperature differences. The mathematical model, which has been discretized, is the closed system obtained by combining the Navier-Stokes equations, the heat transfer equation, the diffusion equations, and an equation relating the fluid density to both the chemical concentration and the temperature. The numerical method is based on the marker-and-cell method, which has been extended to consider the volume expansion due to heat transfer and the density variations.     

The crystal and molecular structure of the tetraethylammonium salt of tetrahydridopentadecacarbonyltetrarhenate(2−) in two crystallographic forms

The structure of the title compound, (NEt₄)₂[H₄Re₄(CO)₁₅], is reported in two crystallographic modifications, I and II. Both forms axe monoclinic and the cell constants are as follows: I, a 11.355(2), b 21.204(4), c 17.416(3) Å, β 94.15(2)°, space group P2₁/c; II, a 21.831(4), b 17.584(3), c 11.446(2) Å, β 96.02(2)°, space group P2₁,/n. Two sets of 3042 (I) and 2870 (II) independent diffraction intensities, collected by counter methods, were used for the solution and refinement of the two structures. The final conventional R factors have values 5.5% (I) and 6.3% (II), respectively. The crystal packings are compared, showing different conformations of the (NEt₄)⁺ cations. The anions contain a tetrametal cluster formed by an isosceles triangle plus an apically bound metal atom; the carbonyl groups are all terminally bonded to the rhenium atoms. Some differences, present both in the metal atom clusters and in the carbonyl dispositions, are discussed and compared with a third, previously reported, crystallographic modification of the same compound.