Experimental study for adsorption and photocatalytic reaction of ethyl methylphosphonate molecule as organophosphorus compound adsorbed at surface of titanium dioxide under UV irradiation in ambient condition

The adsorption and photocatalytic degradation of Ethyl methylphosphonate (EMPA) on powdery TiO₂ film has experimentally investigated using attenuated total reflection-infrared Fourier transform spectroscopy (ATR-FTIR) in ambient condition. Characteristic IR frequency as P-O-C vibration mode as EtO was observed by EMPA adsorbed at the surface of TiO₂. By TiO₂ photocatalysis, the adsorbed EMPA was decomposed to methyl phosphonic acid and phosphoric acid. The increment of IR intensity of which is assigned to Ti–O-P-O-Ti of EMPA was accompanied with increasing the IR peak intensity assigned to MPA. About that, we suggest that the appearance of the Ti–O-P-O-Ti of EMPA by the TiO₂ photocatalysis is regarded as acceleration of the hydrolysis of EMPA by the surface OH groups of TiO₂. The plausible adsorption structure and the photocatalytic reaction mechanism of EMPA at the surface of TiO₂ photocatalyst were elucidated.

     

Integral Kernel Operators on Fock Space – Generalizations and Applications to Quantum Dynamics

A general theory of operators on Boson Fock space is discussed in terms of the white noise distribution theory on Gaussian space (white noise calculus). An integral kernel operator is generalized from two aspects: (i) The use of an operator-valued distribution as an integral kernel leads us to the Fubini type theorem which allows an iterated integration in an integral kernel operator. As an application a white noise approach to quantum stochastic integrals is discussed and a quantum Hitsuda–Skorokhod integral is introduced. (ii) The use of pointwise derivatives of annihilation and creation operators assures the partial integration in an integral kernel operator. In particular, the particle flux density becomes a distribution with values in continuous operators on white noise functions and yields a representation of a Lie algebra of vector fields by means of such operators.     

Interfacial adsorption state of protonated lipophilic porphyrins in a liquid-liquid system by using reflection spectrometry.

Analysis by reflection spectrometry was performed to clarify the interfacial adsorption of protonated lipophilic tetraphenylporphyrin derivatives in a dodecane-aqueous sulfuric acid system, and to confirm the utility of partial reflection spectroscopy. Interfacial adsorption was not observed for porphyrins substituted at the 2,6 positions of meso-phenyl groups, suggesting that the substituents prevent porphyrins from forming aggregates by steric hindrance. Polymorphous J-aggregates of acid dications were produced by tetra-p-tolylporphyrin with a saturated interfacial molecular density of 1.0 x 10(-10) mol cm(-2), which could yield 48 degrees as a mean tilting angle of the pyrrole ring plane from the interface normal. Partial-reflection spectrometry can provide sensitive detection and molecular orientation analysis of interfacial adsorbates.     

Rate coefficient for the reaction of CCl3 radicals with ozone

The rate coefficient for the reaction of CCl₃ radicals with ozone has been measured at 303 ± 2 K. The CCl₃ radicals were generated by the pulsed laser photolysis of carbon tetrachloride at 193 nm. The time profile of CCl₃ concentration was monitored with a photoionization mass spectrometer. Addition of the O₃–O₂ mixture to this system caused a decay of the CCl₃ concentration because of the reactions of CCl₃ + O₃ → products (5) and CCl₃ + O₂ → products (4). The decay of signals from the CCl₃ radical was measured in the presence and absence of ozone. In the absence of ozone, the O₃–O₂ mixture was passed through a heated quartz tube to convert the ozone to molecular oxygen. Since the rate coefficient for the reaction of CCl₃ + O₂ could be determined separately, the absolute rate coefficient for reaction ( 5 ) was obtained from the competition among these reactions. The rate coefficient determined for reaction ( 5 ) was (8.6 ± 0.5) × 10^?13 cm³ molecule^?1 s^?1 and was also found to be independent of the total pressure (253–880 Pa of N₂). This result shows that the reaction of CCl₃ with O₃ cannot compete with its reaction with O₂ in the ozone layer. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 310–316, 2003     

Two-mass models of the vocal cords for natural sounding voice synthesis

Three new two-mass models of the vocal cords are treated. First, the features, structure, and differential equations of motion are described for each of the new models and compared with those of previous models. Second, performances of the models are discussed in terms of glottal volume flow, glottal area, radiated sound pressure, trajectories of mass movement, running spectra of the output sound pressure, and perceptual naturalness of the output sound. Finally, the major effects of glottal source-vocal tract interaction including skewing, truncation, and superposition are investigated, using one of the simplest types of two-mass models and two types of load representing the vocal tract.     

Time-resolved fluorescence spectra of a bichromophoric molecule, 2-methyl-1,2,3,4-tetrahydroisoquinoline in various media

Time-resolved fluorescence spectra of a title molecule (with benzene and aliphatic amine parts) in various media, after excitation by several lasers were observed to complement the previous work by conventional spectroscopy [N. Kanamaru, J. Tanaka, J. Phys. Chem. 95 (1991) 6441]. Though complex with many new features, the results were roughly consistent with the previous ones. The significant conclusions are as follows: (1) The emission to be ascribed to the amine (N) part, with more than one component (of nN and aN types) is observed not only for the acetonitrile solution (as previously reported) but also for all the other media. (2) Contrary to the case of a nonpolar hexane solution, both of N fluorescences in the other media reveal unusually long-lived decay components. This can be interpreted by assuming the so-called charge-transfer-to-solvent (CTTS) state that is nonfluorescent and lies just below the fluorescent state. (3) This observation in the protic media can also be taken as another evidence of the peculiar hydrogen bonding between this amine and the protic solvent molecules [N. Kanamaru, J. Tanaka, J. Phys. Chem. 95 (1991) 6441]. (4) Thus, the unexpectedly large quantum yields of N fluorescences in the polar media are now interpreted as arising due to the slow S₁^N→(CTTS)→S₀ internal conversions.     

A compact optical heterodyne interferometer by optical integration and its application

A compact high-resolution optical heterodyne interferometer combining a two-frequency light module and a minute optical system is described. The light module, which generates two independent frequencies of light, is fabricated by proton exchange method on LiNbO₃ substrate. We report an experiment evaluating measurement accuracy using a micro-displacement measurement system which incorporates this interferometer. Results of the experiment with a standard thickness sample show high thermal stability with maximum measurement error of 1.8 nm at a temperature from 19°C to 33°C. The system was used to measure the hysteresis of a piezoelectric element for displacements of several nm, thereby making it possible to analyze the system quantitatively in practice.     

Spherical dye-doped silica particles

Organic dyes such as water soluble porphyrins were incorporated into monodispersed SiO₂ particles using the sol-gel technique (the Stober synthesis) and their monomeric and dimeric properties were investigated by aiming at the microcavity effect. Doping efficiencies of dyes into SiO₂ particles depended on dye's hydrophilic properties. The doping efficiency of a porphyrin, TTMAPP, decreased with increasing the nominal content in the starting solution and the doping content showed the maximum value of 1.6×10^–5 mol/g SiO₂. With increasing the TTMAPP content, spectra of doped particles were changed from dimeric to monomeric nature; the absorption peak due to dimers disappeared and halfwidth of absorption at Soret band decreased. This unusual change was caused by the decrease of particle sizes by dye doping. The TTMAPP-doped sample having monomeric spectrum showed the fluorescence life time of 8.5 nsec and photochemical hole burning at about 5 K.