Ab initio and density functional theory studies on the mechanism of nucleophilic vinylic substitution of 4<Emphasis Type="Italic">H</Emphasis>-pyran-4-one and 2-methyl-4<Emphasis Type="Italic">H</Emphasis>-pyran-4-one with ammonia

 Nucleophilic vinylic substitutions of 4H-pyran-4-one and 2-methyl-4H-pyran-4-one with ammonia were calculated by the B3LYP method using the 6-31G(d,p) basis set. Bulk solvent effects of aqueous solution were estimated by the polarized continuum and Poisson–Boltzmann self-consistent reaction field models using the 6-311+G(d,p) basis set. In the gas phase different mechanisms were found for the two reaction systems calculated. The reaction of 4H-pyran-4-one proceeds through enol, whereas a feasible path for the less reactive 2-methyl-4H-pyran-4-one is the mechanism through a keto intermediate. Addition of ammonia in concert with proton transfer is the rate-determining step ofthe reaction. The mechanism proceeding either by a bimolecular nucleophilic substitution (S_N2) or by one involving a tetrahedral zwitterionic intermediate is shown to be unlikely in the gas phase or nonpolar solution. The effects of bulk solvent not only consist in a reduction of the various activation barriers by about 25–40 kJ mol⁻¹ but also in a change in the reaction mechanism. Received 26 May 2002 / Accepted 26 July 2002 / Published online: 14 February 2003     

Effect of non-planarity on the spin distribution in the radical anions containing the stilbene or the azobenzene π-system: An ESR and ENDOR Study

The radical anions of 5H-dibenzo[a,d]cycloheptene ( 9 ), 5 H-dibenzo[c,f][1,2]diazepine ( 10 ), 5,6-dihydrodibenzo[a,e]cyclooctene ( 11 ), 5,6-dihydrodibenzo[c,g][1,2]diazocine ( 12 ), and (E)-2,2,5,5-tetramethyl-3,4-diphenylhex-3-ene ( 13 ) were characterized by ESR and ENDOR spectroscopy. Their hyperfine data were compared with those previously reported for radical anions also containing the stilbene or the azobenzene π-system. Whereas the π-spin distribution in the radical anions of the stilbene series is only moderately sensitive to deviations of the π-system from planarity, the radical anions of the azobenzene series respond to steric strain by shifting the π-spin population from the benzene rings to the azo group. This finding is impressively demonstrated by the similar hyperfine data for 9 ^{· ?} and 11 ^{· ?} which contrast with the strongly highly hindered 13 ^{· ?}. A. plausible interpretation is readily provided by the electron affinities of the constituent π-moieties in stilbene and azobenzene. While those of benzene and ethene are both comparatively low, the azo group has a considerably higher electron affinity.     

Pd@SnO2 and SnO2@Pd Core@Shell Nanocomposite Sensors

Pd@SnO₂ and SnO₂@Pd core@shell nanocomposites are prepared via a microemulsion approach. Both nanocomposites exhibit high‐surface, porous matrices of SnO₂ shells (>150 m² g^?1) with very small SnO₂ crystallites (<10 nm) and palladium (Pd) nanoparticles (<10 nm) that are uniformly distributed in the porous SnO₂ matrix. Although similar by first sight, Pd@SnO₂ and SnO₂@Pd are significantly different in view of their structure with Pd inside or outside the SnO₂ shell and in view of their sensor performance. As SMOX‐based sensors (SMOX: semiconducting metal oxide), both nanocomposites show a very good sensor performance for the detection of CO and H₂. Especially, the Pd@SnO₂ core@shell nanocomposite is unique and shows a fast response time (τ₉₀ < 30 s) and a very good response at low temperature (<250 °C), especially under humid‐air conditions. Extraordinarily high sensor signals are observed when exposing the Pd@SnO₂ nanocomposite to CO in humid air. Under these conditions, even commercial sensors (Figaro TGS 2442, Applied Sensor MLC, E2V MICS 5521) are outperformed.     

Metallic graded photonic crystals for graded index lens

We have designed a flat graded index lens made from a metallic graded 2D photonic crystal. The gradient of index has been obtained by varying the filling factor of a flat slab of photonic crystal in the direction perpendicular to that of the propagation of the electromagnetic field. This gradient has been designed in such a way that the flat slab focuses a plane wave. With applications in the microwave range in view, we considered a photonic crystal which consists of copper strips.