High-energy collision-induced dissociation of small polycyclic aromatic hydrocarbons

High-energy collision-induced dissociation (CID) experiments on polycyclic aromatic hydrocarbons (PAHs) having 2-6 rings, naphthalene, anthracene, phenanthrene, fluoranthene, pyrene and coronene, were performed, and the relative abundances of their fragment ions were investigated as a function of collision energy. The results revealed that the PAHs except naphthalene showed a bimodal-type distribution of positive fragmentation ions, which is closely similar to the fragment-ion distribution reported for the CID of three-dimensional fullerene, C(60)(+) and C(70)(+). The three-ring isomers of anthracene and phenanthrene and the four-ring isomers of fluoranthene and pyrene can be distinguishable in their spectra under an electron ionization energy of 70 eV, but the high-energy CID spectra of the three- and four-ring isomers were almost identical. The fragmentation corresponding to fragment ions in the low-mass region of the bimodal CID spectra could be interpreted by the simple statistical model that fragment ions are formed by random evaporation from the molecular ions after a considerable structural rearrangement, 'phase transition', occurring at some high-energy state.     

Regio-specific total synthesis of (±)-2-hydroxyaklavinone

The tricyclic quinone 8 was successfully synthesized from naphthazalin, and the total synthesis of (±)-2-hydroxyaklavinone via 8 was accomplished in an overall yield of about 18% through the regio-controlled route.     

Coherent and incoherent dynamics of excitons in semiconductor microcavities

Il Nuovo Cimento D - We have investigated the dynamics of impulsively excited planar microcavities in the strongly couple regime. With resonant, coherent excitation, the emitted light shows...     

Artificial polarization anomalies from holographic gratings

An aluminum reflection grating made holographically was found to display polarization anomalies when illuminated with p-polarized light. Additional anomalies were detected for both p- and s-polarizations after the grating was coated with a layer of dielectric (410 nm of photoresist). These new anomalies have been interpreted in terms of the optical guided modes of a thin film dielectric waveguide bounded on one side by metal and on the other by vacuum.     

Network images of drainage channels in sea spray icing by MR microscopy

An MR imaging system was developed to visualize brine drainage channels in sea spray icing. Brine pockets trapped in spray-ice matrices during ice growth are structural features of sea spray icing. Brine in the spray ice sample had drained out; therefore, using a suction pump, we filled the air gaps in the drainage channels with dodecane. In the experiments, 0.5-1.0 h was necessary to accumulate signals sufficient to obtain a 3-D micro-image; the image matrix comprised 128(3) voxels (each voxel was 200 microm per side). The MIP view showed that sea spray icing has a developed drainage-channel network structure.     

Detection of macroscopic entanglement by correlation of local observables

We propose a correlation of local observables on many sites in macroscopic quantum systems. By measuring the correlation one can detect, if any, superposition of macroscopically distinct states, which we call macroscopic entanglement, in arbitrary quantum states that are (effectively) homogeneous. Using this property, we also propose an index of macroscopic entanglement.     

Photoelectrochemical decomposition of water on nanocrystalline BiVO4 film electrodes under visible light

The nanocrystalline BiVO4 film electrode on conducting glass showed an excellent efficiency (IPCE = 29% at 420 nm) for the decomposition of water under visible light.     

Ruthenium(II)-catalyzed selective intramolecular [2 + 2 + 2] alkyne cyclotrimerizations

In the presence of a catalytic amount of Cp*RuCl(cod), 1,6-diynes chemoselectively reacted with monoalkynes at ambient temperature to afford the desired bicyclic benzene derivatives in good yields. A wide variety of diynes and monoynes containing functional groups such as ester, ketone, nitrile, amine, alcohol, sulfide, etc. can be used for the present ruthenium catalysis. The most significant advantage of this protocol is that the cycloaddition of unsymmetrical 1,6-diynes with one internal alkyne moiety regioselectively gave rise to meta-substituted products with excellent regioselectivity. Completely intramolecular alkyne cyclotrimerization was also accomplished using triyne substrates to obtain tricyclic aromatic compounds fused with 5-7-membered rings. A ruthenabicycle complex relevant to these cyclotrimerizations was synthesized from Cp*RuCl(cod) and a 1,6-diyne possessing phenyl terminal groups, and its structure was unambiguously determined by X-ray analysis. The intermediary of such a ruthenacycle intermediate was further confirmed by its reaction with acetylene, giving rise to the expected cycloadduct. The density functional study on the cyclotrimerization mechanism elucidated that the cyclotrimerization proceeds via oxidative cyclization, producing a ruthenacycle intermediate and subsequent alkyne insertion initiated by the formal [2 + 2] cycloaddition of the resultant ruthenacycle with an alkyne.