Structure of host-guest complexes between dibenzo-18-crown-6 and water, ammonia, methanol, and acetylene: evidence of molecular recognition on the complexation

Complexes of dibenzo-18-crown-6 (DB18C6, host) with water, ammonia, methanol, and acetylene (guest) in supersonic jets have been characterized by laser induced fluorescence (LIF), UV-UV hole-burning (UV-UV HB), and IR-UV double resonance (IR-UV DR) spectroscopy. Firstly, we reinvestigated the conformation of bare DB18C6 (species m1 and m2) and the structure of DB18C6-H(2)O (species a) [R. Kusaka, Y. Inokuchi, T. Ebata, Phys. Chem. Chem. Phys., 2008, 10, 6238] by measuring IR-UV DR spectra in the region of the methylene CH stretching vibrations. The IR spectral feature of the methylene CH stretch of DB18C6-H(2)O is clearly different from those of bare DB18C6 conformers, suggesting that DB18C6 changes its conformation when forming a complex with a water molecule. With the aid of Monte Carlo simulation for extensive conformational search and density functional calculations (M05-2X/6-31+G*), we reassigned species m1 and m2 to conformers having C(1) and C(2) symmetry, respectively. Also, we confirmed the DB18C6 part in species a of DB18C6-H(2)O to be "boat" conformation (C(2v)). Secondly, we identified nine, one, and two species for the DB18C6 complexes with ammonia, methanol, and acetylene, respectively, by the combination of LIF and UV-UV HB spectroscopy. From the IR spectroscopic measurement in the methylene CH stretching region, a similar conformational change was identified in the DB18C6-ammonia complexes, but not in the complexes with methanol or acetylene. The structures of all the complexes were determined by analyzing the electronic transition energies, exciton splitting, and IR spectra in the region of the OH, NH, and CH stretching vibrations. In DB18C6-ammonia complexes, an ammonia molecule is incorporated into the cavity of the boat conformation by forming "bifurcated" and "bidentate" hydrogen-bond (H-bond), similar to the case of the DB18C6-H(2)O complex. On the other hand, in the DB18C6-methanol and -acetylene complexes, methanol and acetylene molecules are simply attached to the C(1) and C(2) conformations, respectively. From the difference of the DB18C6 conformations depending on the type of the guest molecules, it is concluded that DB18C6 distinguishes water and ammonia from methanol and acetylene when it forms complexes, depending on whether guest molecules have an ability to form bidentate H-bonding.     

Fabrication of BDD quantum node switches on embedded GaAs quantum wires grown by selective MBE

In view of applications to hexagonal binary decision diagram (BDD) LSIs, a first attempt is made to form quantum BDD node switches on selectively grown (SG) embedded quantum wires (QWRs) by molecular beam epitaxy (MBE). SG branch switches controlled by a Schottky wrap gate (WPG) were successfully fabricated by MBE growth and subsequent device processing. Gate control characteristics were studied by gate-dependent Shubnikov–de-Haas measurements, and the behavior was found to be similar to that of devices fabricated on wires by etching. The switch exhibited clear conductance quantization at low temperature, and temperature dependence of the voltage slope of conductance jump was clarified. A Y-branch BDD node device using two SG branch switches was successfully fabricated, and realized clear path switching characteristics.     

Electrical conductivity of cytochrome c anhydrous film

Electrical conducitivities of both ferricytochrome c and ferrocytochrome c anhydrous films were measured at physiological temperatures. A film-casting method was applied to prepare the films. Rather low values of resistivities (55°C) of 6.5 × 10¹⁰ Ω cm for ferrocytochrome c in comparison with the previously reported value of 10¹¹ Ω cm (127°C) were obtained. Apparent activation energies for the above conductivities, 0.6 eV, were the same in both samples.     

Mechanism of stigmasterol dealkylation in insect

Deuterated stigmasterols (10, 11 and 12) were chemically synthesized and fed to silk-worm larvae. GC-MS analysis of the metabolites, cholesterol (4) and desmosterol (6), indicates the migration of 25-hydrogen to C-24 position during stigmasterol dealkylation. 22,24(28)-Dienes(8a and 8b) were shown to be converted to 22,24-diene (5), desmosterol and cholesterol.