Oxidation of Dimethyl Sulfide in Air Using Electron-Beam Irradiation,and Enhancement of its Oxidation Via an MnO<Subscript>2</Subscript> Catalyst

The decomposition of dimethyl sulfide (DMS) at initial concentrations of 4.5–18.0 ppmv in air was studied under electron-beam (EB) irradiation. Doses to decompose 90% of input DMS were 2.5 kGy for 4.5 ppmv, 3.4 kGy for 10.6 ppmv, and 3.9 kGy for 18.0 ppmv. HCOOH, (CH₃)₂SO, and trace CH₃OH and (CH₃)₂SO₂ were produced as irradiation products in addition to CO₂ and CO. Application of an O₃ decomposition catalyst to an irradiated sample gas led to an enhancement in the oxidation of DMS and its products into CO₂ and the decomposition of O₃. For 10.6 ppmv DMS/air, the mineralization ratio increased from 41% via only EB irradiation to 100% via the combination treatment at 6.3 kGy. The yield of CO₂ to CO_x increased from 5.3 to 87.6% by combination with catalytic oxidation. This combination treatment enables the irradiation energy used to deodorize gas streams containing DMS to be reduced.     

Finite-Difference Time-Domain Analysis of the Interaction of Gaussian Evanescent Light with a Single Dielectric Sphere or Ordered Dielectric Spheres

The interaction of gaussian evanescent light with a single dielectric sphere or ordered dielectric spheres in an attenuated total reflection (ATR) geometry was analyzed by the finite-difference time-domain method. Various aspects of this interaction were investigated in terms of spatial visualizations of light intensity, reflectance vs. wavelength characteristics, the transient behavior of reflectances, and so forth. In the case of a single sphere, it was evident that the whispering gallery mode can be excited in ATR geometries, but such excitation cannot be easily confirmed only through the observation of wavelength-scanned ATR spectra. In the case of a closely packed two-dimensional array of dielectric spheres, it was found that an easy axis and also a difficult axis for light propagation exist.This paper was originally presented at the 5th International Conference on NEAR FIELD OPTICS and RELATED TECHNOLOGIES (NFO-5), which was held on December 6–10, 1998 at Coganoi Bay Hotel, Shirahama, Japan, in cooperation with the Japan Society of Applied Phisics and Mombusho Grantin Aid for Scientific Research on Priority Areas “Near-field Nano-optics” Project, sponsored by Japan Society for the Promotion of Science.     

Prehomogeneous vector spaces and ergodic theory II

We apply M. Ratner's theorem on closures of unipotent orbits to the study of three families of prehomogeneous vector spaces. As a result, we prove analogues of the Oppenheim Conjecture for simultaneous approximation by values of certain alternating bilinear forms in an even number of variables and certain alternating trilinear forms in six and seven variables.

     

Uptake of transition metal ions using liposomes containing dicetylphosphate as a ligand.

The uptake of Cu2+ was investigated using various types of liposomes composed of phosphatidylcholine (PC), cholesterol (Chol) and dicethylphosphate (DCP). DCP played a role as a ligand for Cu2+. Multilamellar vesicles (MLVs) were more effective for the uptake of Cu2+ compared to unilamellar vesicles prepared by the extrusion technique. The uptake efficiency of MLVs for Cu2+ was dependent on the molar ratio of DCP in MLVs. The uptake percent of Cu2+ was 92% using MLVs having a PC:DCP:Chol molar ratio of 4:3:3; 95% of the total vesicle Cu2+ was bound to DCP of the outer membrane surface of the MLVs, and the remaining 5% of the total Cu2+ was distributed into the interior side of the MLVs. MLVs having a PC:DCP:Chol molar ratio of 4:3:3 were also effective as separation media for Mn2+, Co2+, Ni2+ and Zn2+. The uptake efficiency of the MLVs for the transition-metal ions increased in the order Co2+ < Zn2+ < Ni2+ < Mn2+ < Cu2+.     

Magnetic circular dichroism study of directly fused porphyrins.

The magnetic circular dichroism (MCD) spectra of doubly and triply linked fused bisporphyrins (2MD and 2MT, M = Ni, Zn, Cu, Pd, and H2) and triply linked higher oligomers (3ZnT and 4ZnT) have been measured, and their Q-bands assigned based on the results of INDO/s calculations. In contrast to the Faraday A term observed for the Q(0,0) band of Ni(II) tetraphenylporphyrin, a single positive Faraday B term was observed for the lowest energy transition of the fused systems. The calculations indicated that the molecular orbitals (MOs) of the directly fused porphyrins consist of linear combinations of the constituent monomeric MOs, and that the effect of lowering the symmetry is always larger on the lowest unoccupied molecular orbital (LUMO) than on the highest occupied molecular orbital (HOMO). On the basis of Michl's perimeter model, these features can be correlated with the observed positive MCD signs in the near infrared region. A weak absorption band at 600-700 nm for the fused dimers can be assigned to a short-axis polarized Q transition.     

Molecular distortion effect on ff-emission in a Pr(III) complex with 4,7-diphenyl-1,10-phenanthroline.

The electronic and structural behaviour of a Pr(III) complex with 4,7-diphenyl-1,10-phenanthroline, [Pr(bathophen)(2)(NO(3))(3)], is investigated with respect to the effect of configuration changes on the Pr(III) centre. [Pr(bathophen)(2)(NO(3))(3)] luminesces from the excited states of the ligand and the metal ion. The fluorescence, ff-emission ((1)D(2)-->(3)H(4)), and phosphorescence bands appear at 394, 608.2 and 482 nm, respectively, in the solid state. In acetonitrile, the complex also shows multiple emissions. From the time-resolved emission and the lifetime measurements, the excitation energy-transfer in [Pr(bathophen)(2)(NO(3))(3)] is clarified, that is, the upper excited triplet level of the ligand acts as an energy donor, while the (1)D(2) levels of Pr(III) is the acceptor. Additionally, the emission phenomena of the complex can be modified by molecular distortion, particularly by rotation of the phenyl groups in the ligand.     

Efficient optical near-field energy transfer along an Au nanodot coupler with size-dependent resonance

We confirmed that the light intensity (λ=785 nm) scattered from an isolated hemispherical Au nanoparticle was resonantly enhanced at a diameter of 200 nm and a height of 50 nm, as observed experimentally using a collection-mode near-field optical microscope. The experimental results agreed with the calculated results using Mie’s theory. Furthermore, we observed resonant energy transfer of the optical near-field energy along a chain of Au nanoparticles. The magnitude of the transferred energy increased resonantly at the size of resonant light scattering for an isolated Au nanoparticle (200 nm diameter with 240 nm center-to-center separation). PACS 42.82.Et; 73.20.Mf; 78.67.Bf     

Optical pulsation mechanism based on optical near-field interactions

We theoretically demonstrate optical pulsation based on optical near-field interactions between quantum nanostructures. It is composed of two quantum dot systems, each of which consists of a combination of smaller and larger quantum dots, so that optical excitation transfer occurs. With an architecture in which the two systems take the role of a timing delay and frequency up-conversion, we observe pulsation in populations pumped by continuous-wave light irradiation. The pulsation is induced with suitable setting of parameters associated with the optical near-field interactions. This will provide critical insights toward the design and implementation of experimental nanophotonic pulse generating devices.