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71.
Tachikawa T Takai Y Tojo S Fujitsuka M Irie H Hashimoto K Majima T 《The journal of physical chemistry. B》2006,110(26):13158-13165
The photocatalytic degradation processes of ethylene glycol (EG) during the UV or visible light irradiation of pure anatase and nitrogen (N)-doped TiO2 powders (TiO(2-x)N(x), x = 0, 0.002, 0.003, and 0.007) were investigated using time-resolved diffuse reflectance (TDR) and solid-state NMR spectroscopies. The TDR spectra and time traces observed for the charge carriers indicated that the scavenging of photogenerated holes (h+) by EG occurred during the 355-nm laser photolysis of the N-doped TiO2 powders, while no direct oxidation reaction of EG by h+ occurred during the 460-nm laser photolysis, although the charge carriers were sufficiently generated upon excitation. The solid-state magic-angle spinning (MAS) NMR measurements revealed that EG is preferentially chemisorbed on the surface of the N-doped TiO2 powders, in contrast to the pure TiO2, and degrades under visible light irradiation. 相似文献
72.
Tachikawa T Tojo S Fujitsuka M Sekino T Majima T 《The journal of physical chemistry. B》2006,110(29):14055-14059
The photocatalytic one-electron oxidation reaction of an aromatic compound during UV light irradiation of titania nanotubes and nanoparticles was investigated using time-resolved diffuse reflectance spectroscopy. Remarkably long-lived radical cations of the aromatic compound and trapped electrons were observed for the nanotubes when compared to those for nanoparticles. The influences of the morphology on the one-electron oxidation process of an aromatic compound adsorbed on the surface were discussed in terms of the charge recombination dynamics between the radical cation and electrons in TiO2. 相似文献
73.
Reflection spectra of silicate glasses were measured in the spectral region 2–13 eV. The bands due to bridging oxygen were found at 11.6 and 10.4–9.5 eV. The bands for non-bridging oxygens were found in the region 8.8–4.9 eV. They shift to lower energy with increasing ionic radius for the low valency cations while they shift to higher energy with increasing ionic radius for the high valency cations. The correlation between the measured bands and the absorption wavelength calculated from Drude-Voigt dispersion formula is discussed. 相似文献
74.
75.
Cho DW Fujitsuka M Yoon UC Majima T 《Physical chemistry chemical physics : PCCP》2008,10(30):4393-4399
The intermolecular photoinduced electron transfer (PET) processes of 1,8-naphthalimide (NI) derivatives including NI-linker-phenothiazine dyads were investigated in a protic H(2)O/CH(3)CN (v/v=1:1) solvent using ns-laser flash photolysis with 355 nm-laser excitation. NI derivatives are surrounded by H(2)O in the ground state in H(2)O/CH(3)CN. The T(1)-T(n) absorption band of (3)NI* was observed at around 470 nm. The transient absorption band at around 410 nm increased concomitantly with the decay of (3)NI* in H(2)O/CH(3)CN. This implies that hydrated NI anion radical (NI*(-)) is primarily generated via the quenching of (3)NI* by NI at the diffusion control rate. This intermolecular PET did not occur in aprotic CH(3)CN. The formation and decay times of NI*(-) showed strong dependence on the concentration of NI. Then, we suggest that NI*(-) could undergo proton abstraction to give ketyl radical species of NI [NI(H)*] in H(2)O/CH(3)CN. 相似文献
76.
Yamaji M Cai X Sakamoto M Fujitsuka M Majima T 《The journal of physical chemistry. A》2008,112(45):11306-11311
Photochemical properties of p-phenylphenacyl derivatives (PP-X) having C-halide, C-S, and C-O bonds in the lowest (T 1) and higher (T n ) triplet excited states were investigated in solution by using single-color and stepwise two-color two-laser flash photolysis techniques. PP-Xs (X = Br, SH, and SPh) undergo beta-bond dissociation in the lowest singlet excited states (S 1) while the C-X bonds of other PP-Xs are stable upon 266-nm laser photolysis. The T 1(pi,pi*) states of PP-X were efficiently produced during 355-nm laser photolysis of benzophenone as a triplet sensitizer. Triplet PP-Xs deactivate to the ground state without photochemical reactions. Upon 430-nm laser photolysis of the T 1 states of PP-X (X = Br, Cl, SH, SPh, OH, OMe, and OPh), decomposition of PP-X in the T n states was found. On the basis of the changes in the transient absorption, quantum yields (Phi dec) of the decomposition of PP-X in the T n states were determined, while bond dissociation energies (BDE) of the C-X bonds were calculated by computations. According to the relationship between the Phi dec and BDE values, it was shown that the decomposition of PP-X in the T n state is due to beta-cleavage of the corresponding C-X bond, and that the state energy of the reactive T n for the C-O bond cleavage differs from that for the C-halide and C-S bond cleavage. The reaction profiles of the C-X bond cleavage of PP-X in the T n states were discussed. 相似文献
77.
Nishimura N Tanikawa J Fujii M Kawahara T Ino J Akita T Fujino T Tada H 《Chemical communications (Cambridge, England)》2008,(30):3564-3566
MnO(2) nanoparticle-loaded TiO(2) prepared by a green process capable of removing harmful MnO(4)(-) ions from water exhibits catalytic activity for a test reaction, H(2)O(2) decomposition, in the dark with its activity enhanced by UV light irradiation. 相似文献
78.
Novel method for obtaining homogeneous giant vesicles from a monodisperse water-in-oil emulsion prepared with a microfluidic device 总被引:3,自引:0,他引:3
Sugiura S Kuroiwa T Kagota T Nakajima M Sato S Mukataka S Walde P Ichikawa S 《Langmuir : the ACS journal of surfaces and colloids》2008,24(9):4581-4588
A novel technique called the "lipid-coated ice droplet hydration method" is presented for the preparation of giant vesicles with a controlled size between 4 and 20 microm and entrapment yields for water-soluble molecules of up to about 30%. The method consists of three main steps. In the first step, a monodisperse water-in-oil emulsion with a predetermined average droplet diameter between 4 and 20 microm is prepared by microchannel emulsification, using sorbitan monooleate (Span 80) and stearylamine as emulsifiers and hexane as oil. In the second step, the water droplets of the emulsion are frozen and separated from the supernatant hexane solution by precipitation, followed by a removal of the supernatant and followed by the replacement of Span 80 by using a hexane solution containing egg yolk phosphatidylcholine, cholesterol, and stearylamine (5:5:1, molar ratio). This procedure is performed at -10 degrees C to keep the water droplets of the emulsion in a frozen state and thereby to avoid extensive water droplet coalescence. In the third step, hexane is evaporated at -4 to -7 degrees C and an external water phase is added to the remaining mixture of lipids and water droplets to form giant vesicles that have an average size in the range of that of the initial emulsion droplets (4-20 microm). The entrapment yield and the lamellarity of the vesicles obtained depend on the lipid/water droplet ratio and on the composition of the external water phase. At high lipid/water droplet ratio, the giant vesicles have a thicker membrane (indicating multilamellarity) and a higher entrapment yield than in the case of a low lipid/water droplet ratio. The highest entrapment yield ( approximately 35%) is obtained if the added external water phase contains preformed unilamellar egg phosphatidylcholine vesicles with an average diameter of 50 nm. The addition of these small vesicles minimizes the water droplet coalescence during the third step of the vesicle preparation, thereby decreasing the extent of release of water-soluble molecules originally present in the water droplets. The GVs prepared can be extruded through polycarbonate membranes to yield large unilamellar vesicles with about 100 nm diameter. This size reduction, however, leads to a decrease in the entrapment yield to about 12% due to solute leakage from the vesicles during the extrusion process. 相似文献
79.
We developed a TEMPO-bound dithiolate ligand (= tempodt) and its Pt(diimine)(dithiolate) complex to realize a unique electronic structure with the potential for unprecedented functionalities. The physical properties and electronic structures of tempodt, (tempodt)Pt, and their related compounds were investigated by cyclic voltammetry, UV-visible spectroscopy, electron spin resonance (ESR) spectroscopy, and other techniques. It was revealed that (tempodt)Pt showed an unusual electronic structure in which the HOMO level (= pi-conjugated dithiolate-based orbital) was located above the SOMO level attributed to the TEMPO moiety, and that this situation was achieved via a drastic electronic structure change of SOMO-HOMO level conversion through complex formation. These findings were further supported by an investigation into a one-electron oxidized (tempodt)Pt and related complexes. 相似文献
80.
Kang JH Asai D Kim JH Mori T Toita R Tomiyama T Asami Y Oishi J Sato YT Niidome T Jun B Nakashima H Katayama Y 《Journal of the American Chemical Society》2008,130(45):14906-14907
We succeeded in cancer cell specific gene expression by using a polyplex responsive to protein kinase Calpha, which is activated in various types of cancer cells. 相似文献