Electrophilic transannular cyclization of octadehydrodibenzo[12]annulene reexamined: indication of the formation of both anti- and syn-indenofluorenes

The reaction of tetrabutoxyoctadehydrodibenzo[12]annulene 2f with iodine under aerobic conditions was reexamined. Contrary to previous reports, the present results revealed the formation of both anti-diiodoindenofluorenedione and its syn isomer through the oxidation of the respective tetraiodoindenofluorenes, indicating the occurrence of two modes of iodine-induced transannular cyclization. This was supported by the reaction of 2f with bromine, which gave anti- and syn-hexabromodihydroindenofluorenes through interception of indenofluorene intermediates by bromine. The hexabromides were transformed into the corresponding dibromodiones by hydrolysis.     

Three distinct water structures at a zwitterionic lipid/water interface revealed by heterodyne-detected vibrational sum frequency generation

Lipid/water interfaces and associated interfacial water are vital for various biochemical reactions, but the molecular-level understanding of their property is very limited. We investigated the water structure at a zwitterionic lipid, phosphatidylcholine, monolayer/water interface using heterodyne-detected vibrational sum frequency generation spectroscopy. Isotopically diluted water was utilized in the experiments to minimize the effect of intra/intermolecular couplings. It was found that the OH stretch band in the Imχ((2)) spectrum of the phosphatidylcholine/water interface exhibits a characteristic double-peaked feature. To interpret this peculiar spectrum of the zwitterionic lipid/water interface, Imχ((2)) spectra of a zwitterionic surfactant/water interface and mixed lipid/water interfaces were measured. The Imχ((2)) spectrum of the zwitterionic surfactant/water interface clearly shows both positive and negative bands in the OH stretch region, revealing that multiple water structures exist at the interface. At the mixed lipid/water interfaces, while gradually varying the fraction of the anionic and cationic lipids, we observed a drastic change in the Imχ((2)) spectra in which spectral features similar to those of the anionic, zwitterionic, and cationic lipid/water interfaces appeared successively. These observations demonstrate that, when the positive and negative charges coexist at the interface, the H-down-oriented water structure and H-up-oriented water structure appear in the vicinity of the respective charged sites. In addition, it was found that a positive Imχ((2)) appears around 3600 cm(-1) for all the monolayer interfaces examined, indicating weakly interacting water species existing in the hydrophobic region of the monolayer at the interface. On the basis of these results, we concluded that the characteristic Imχ((2)) spectrum of the zwitterionic lipid/water interface arises from three different types of water existing at the interface: (1) the water associated with the negatively charged phosphate, which is strongly H-bonded and has a net H-up orientation, (2) the water around the positively charged choline, which forms weaker H-bonds and has a net H-down orientation, and (3) the water weakly interacting with the hydrophobic region of the lipid, which has a net H-up orientation.     

Comparative analysis and quantitative evaluation of the field of view and the viewing zone of single-shot phase-shifting digital holography using space-division multiplexing

We comparatively analyzed and quantitatively evaluated the field of view and the viewing zone of single-shot phaseshifting digital holography that uses space-division multiplexing, for the first time. We formulated the sampling intervals in the techniques in which the phase of the reference wave is spatially divided into two and four steps, and numerically simulated the areas. It was clarified that each area of the spatial two-step phase-shifting technique was twice as wide as that of the spatial four-step phase-shifting technique. We also experimentally investigated the areas. The ghost appeared for the spatial four-step technique when the object was between the boundary of the field of view of the spatial two-step technique and that of the spatial four-step technique, but did not appear for the spatial two-step technique.     

High-speed phase imaging by parallel phase-shifting digital holography

Parallel phase-shifting digital holography can obtain three-dimensional information of a dynamically moving object with high accuracy by using space-division multiplexing of multiple holograms required for phase-shifting interferometry. We demonstrated high-speed parallel phase-shifting digital holography and obtained images of the phase variation of air caused by a compressed gas flow sprayed from a nozzle. In particular, we found the interesting phenomenon of periodic phase distributions. Reconstructed images were obtained at frame rates of 20,000 and 180,000 frames per second.