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31.
Toshikazu Kaise Hiroshi Yamauchi Yoshiya Horiguchi Takayuki Tani Shigenobu Watanabe Teruhisa Hirayama Shozo Fukui 《应用有机金属化学》1989,3(3):273-277
The acute toxicity of methylarsonic acid, CH3AsO(OH)2 (MAA), dimethylarsininc acid, (CH3)2AsO(OH) (DMAA), and trimethylarsine oxide, (CH3)3AsO (TMAO), were examined in mice with oral administration. The LD50 values of MAA, DMAA and TMAO were 1.8, 1.2 and 10.6 g kg?1 respectively. The toxicity of MAA and DMAA was very much lower than that for inorganic arsenic compounds. It was shown that TMAO has a similar acute toxicity to arsenobetaine. On the other hand, when the mice were administered 14.4 g kg?1 of TMAO once only orally, a garlic-like odor (trimethylarsine, (CH3)3As) was definitely detectable in the exhalation of the animals by the human olfactory sense within about a few minutes. 相似文献
32.
We analyze the effects of inelastic scattering on the tunneling time theoretically, using generalized Nelson’s quantum mechanics.
This generalization enables us to describe quantum system with channel couplings and optical potential in a real time stochastic
approach, which seems to give us a new insight into quantum mechanics beyond Copenhagen interpretation 相似文献
33.
Shimada T Kondoh H Iwasaki M Nakai I Nagasaka M Amemiya K Orita H Ohta T 《The journal of physical chemistry. B》2006,110(41):20507-20512
The adsorption structure of NO on the reconstructed Pt(110)-(1 x 2) surface was studied with X-ray photoelectron spectroscopy (XPS), X-ray photoelectron diffraction (XPD), low-energy scanned-angle photoelectron diffraction (LESA-PD), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The experiments were performed at 180 K, where no surface lifting from (1 x 2) to (1 x 1) takes place after NO adsorption. XPS indicates that the (1 x 2) unit cell of the Pt(110) surface contains 1.5 NO molecules at the saturated coverage. XPD and LESA-PD analyses allow us to propose a structural model for the NO adlayer, where two-thirds of the NO molecules in the (1 x 2) unit cell are adsorbed on the atop site of the close-packed Pt rows (ridges) along the [10] direction with an inclined geometry and one-third of the NO molecules adsorb on the bridge site between the Pt ridges with an upright configuration. This model is supported by the N K-edge NEXAFS experiments and is consistent with the recently reported model based on the density functional theory (Orita, H.; Nakamura, I.; Fujitani, T. J. Phys. Chem. B 2005, 109, 10312). 相似文献
34.
Nobumasa Chaki Dr. Satoru Muramatsu Yuji Iida Seiya Kenjo Prof. Dr. Yoshiya Inokuchi Prof. Dr. Toshifumi Iimori Prof. Dr. Takayuki Ebata 《Chemphyschem》2019,20(8):996-1000
The S1 electronic state of 7,7,8,8-Tetracyanoquinodimethane (TCNQ) has been investigated by laser induced fluorescence (LIF), dispersed fluorescence (DF) spectroscopy, and lifetime measurements under jet-cooled conditions in the gas-phase. The LIF spectrum showed a weak origin band at 412.13 nm (24262 cm−1) with prominent progression and combination bands involving vibrations of 327, 1098, and 2430 cm−1. In addition, very strong bands appeared at ∼363.6 nm (3300 cm−1 above the origin). Both the LIF and DF spectra indicate considerable geometric change in the S1 state. The fluorescence lifetime of S1 at zero-point level was obtained to be 220 ns. This lifetime is 40 times longer than the radiative lifetime estimated from the S1−S0 oscillator strength. Furthermore, the lifetimes of the vibronic bands exhibited drastic energy dependence, indicating a strong mixing with the triplet (T1) or intramolecular charge-transfer (CT) state. This study is thought to disclose intrinsic nature of TCNQ, which has been well known as a component of organic semiconductors and a versatile p-type dopant. 相似文献
35.
The infrared photodissociation spectra of [(CO 2) n (CH 3OH) m ] (-) ( n = 1-4, m = 1, 2) are measured in the 2700-3700 cm (-1) range. The observed spectra consist of an intense broad band characteristic of hydrogen-bonded OH stretching vibrations at approximately 3300 cm (-1) and congested vibrational bands around 2900 cm (-1). No photofragment signal is observed for [(CO 2) 1,2(CH 3OH) 1] (-) in the spectral range studied. Ab initio calculations are performed at the MP2/6-311++G** level to obtain structural information such as optimized structures, stabilization energies, and vibrational frequencies of [(CO 2) n (CH 3OH) m ] (-). Comparison between the experimental and the theoretical results reveals the structural properties of [(CO 2) n (CH 3OH) m ] (-): (1) the incorporated CH 3OH interacts directly with either CO 2 (-) or C 2O 4 (-) core by forming an O-HO linkage; (2) the introduction of CH 3OH promotes charge localization in the clusters via the hydrogen-bond formation, resulting in the predominance of CO 2 (-).(CH 3OH) m (CO 2) n-1 isomeric forms over C 2O 4 (-).(CH 3OH) m (CO 2) n-2 ; (3) the hydroxyl group of CH 3OH provides an additional solvation cite for neutral CO 2 molecules. 相似文献
36.
Horii D Amemiya F Fuchigami T Atobe M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(33):10382-10387
We have developed a novel electrosynthetic system for anodic substitution reactions by using parallel laminar flow in a microflow reactor. This system enables nucleophilic reactions to overcome the restraint, such as the oxidation potential of nucleophiles and the stability of cationic intermediates, by the combined use of ionic liquids as reaction media and the parallel laminar flow in the microflow reactor. By using this novel electrosynthetic system, the anodic substitution reaction of carbamates, especially of cyclic carbamates, with allyltrimethylsilane were carried out to provide the corresponding products in moderate to good conversion yields in a single flow-through operation at ambient temperature (without the need for low-temperature conditions). 相似文献
37.
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39.
Stark effects on the phosphorescence spectra of p-benzoquinone have been studied in naphthalene crystals at temperatures between 1.7 and 30 K. The experimental data establish that the band splitting of 24 cm?1 arises from a double minimum potential in the T1 state. 相似文献
40.
Here we report on the unprecedentedly high resolution imaging of ion transport through single nanopores by scanning electrochemical microscopy (SECM). The quantitative SECM image of single nanopores allows for the determination of their structural properties, including their density, shape, and size, which are essential for understanding the permeability of the entire nanoporous membrane. Nanoscale spatial resolution was achieved by scanning a 17 nm radius pipet tip at a distance as low as 1.3 nm from a highly porous nanocrystalline silicon membrane in order to obtain the peak current response controlled by the nanopore-mediated diffusional transport of tetrabutylammonium ions to the nanopipet-supported liquid-liquid interface. A 280 nm × 500 nm image resolved 13 nanopores, which corresponds to a high density of 93 nanopores/μm(2). A finite element simulation of the SECM image was performed to assess quantitatively the spatial resolution limited by the tip diameter in resolving two adjacent pores and to determine the actual size of a nanopore, which was approximated as an elliptical cylinder with a depth of 30 nm and major and minor axes of 53 and 41 nm, respectively. These structural parameters were consistent with those determined by transmission electron microscopy, thereby confirming the reliability of quantitative SECM imaging at the nanoscale level. 相似文献