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31.
    
We established a gas-phase, elementary reaction model for chemical vapor deposition of silicon carbide from methyltrichlorosilane (MTS) and H2, based on the model developed at Iowa State University (ISU). The ISU model did not reproduce our experimental results, decomposition behavior of MTS in the gas phase in an environment with H2. Therefore, we made several modifications to the ISU model. Of the reactions included in existing models, 236 were lacking in the ISU model, and thus were added to the model. In addition, we modified the rate constants of the unimolecular reactions and the recombination reactions, which were treated as a high-pressure limit in the ISU model, into pressure-dependent rate expressions based on the previous reports (to yield the ISU+ model), for example, H2(+M) → H + H(+M), but decomposition behavior remained poorly reproducible. To incorporate the pressure dependencies of unimolecular decomposition rate constants, and to increase the accuracies of these constants, we recalculated the rate constants of five unimolecular decomposition reactions of MTS using the Rice-Ramsperger-Kassel-Marcus method at the CBS-QB3 level. These chemistries were added to the ISU+ model to yield the UT2014 model. The UT2014 model reproduced overall MTS decomposition. From the results of our model, we confirmed that MTS mainly decomposes into CH3 and SiCl3 at the temperature around 1000°C as reported in the several studies.  相似文献   
32.
Erratum     
Anion-catalyzed phase-transfer catalysis was successfully applied to diazotization of pentafluoroaniline in a dichloromethane-aqueous sulfuric acid two-phase system. The resulting diazonium group was coupled in situ with anisole, 1-methoxynaphthalene, and mesitylene, and replaced in situ with bromo, hydryl, and phenyl substituents under a two-phase condition.  相似文献   
33.
L-Threonine was transformed, stereospecifically, to a versatile β-lactam (5a) in 3 steps. This β-lactam was further converted to a key intermediate (25) for the synthesis of thienamycin and its biologically active analogues. Furthermore, the compound 5a was changed to iodides (18 and 23), cyanides (19 and 24), chloromethylketone (26) and aldehydes (30 and 31) which appear to have a latent potential as precursors for the syntheses of the carbapenems.  相似文献   
34.
35.
Ag nanoparticles were added to DMcT-PAn composites to improve charge-discharge performance of the composites as a cathode material for lithium rechargeable batteries. Addition of Ag nanoparticles successfully enhanced the redox activity of the composites, possibly due to electrocatalytic activity of the nanoparticles. Increased conductivity of the composite films could be another possible origin for the enhanced redox activity. UV/vis spectroscopic analysis suggested strong interactions between DMcT and nanoparticles, while only weak interactions were observed between PAn and nanoparticles. XPS measurements further confirmed the interactions between DMcT and Ag nanoparticles based on a signal indicative of a silver-sulfur bond.  相似文献   
36.
Tetrameric porphyrin formation of 2‐hydroxymethylpyrrole fused with porphyrins through a bicyclo[2.2.2]octadiene unit gave bicyclo[2.2.2]octadiene‐fused porphyrin pentamers. Thermal conversion of the pentamers gave fully π‐conjugated cruciform porphyrin pentamers fused with benzene units in quantitative yields. UV/Vis spectra of fully π‐conjugated porphyrin pentamers showed one very strong Q absorption and were quite different from those of usual porphyrins. From TD‐DFT calculations, the HOMO level is 0.49 eV higher than the HOMO?1 level. The LUMO and LUMO+1 levels are very close and are lower by more than 0.27 eV than those of other unoccupied MOs. The strong Q absorption was interpreted as two mutually orthogonal single‐electron transitions (683 nm: 86 %, HOMO→LUMO; 680 nm: 86 %, HOMO→LUMO+1). The two‐photon absorption (TPA) cross section value (σ(2)) of the benzene‐fused porphyrin pentamer was estimated to be 3900 GM at 1500 nm, which is strongly correlated with a cruciform molecular structure with multidirectional π‐conjugation pathways.  相似文献   
37.
Akai S  Hanada R  Fujiwara N  Kita Y  Egi M 《Organic letters》2010,12(21):4900-4903
The combination of vanadium-oxo compounds (3 or 4) with a lipase produced the regio- and enantioconvergent transformation of racemic allyl alcohols (1 or 2) into optically active allyl esters. In this system, the vanadium compounds catalyzed the continuous racemization of the alcohols along with the transposition of the hydroxyl group, while the lipase effected the chemo- and enantioselective esterification to achieve the dynamic kinetic resolution.  相似文献   
38.
Direct analysis of rocks by laser ablation inductively coupled plasma mass spectrometry is described. Both powdered standard rocks and the original rocks were analysed and the results agreed with each other in spite of the difference in the surface states. Microprobe analysis of biotite in granite JG1 was also done directly with a focused laser beam and the results obtained were very close to the solution values given by the conventional aqueous method using biotite separated from an original rock. For quantitative analysis, the measured signal intensity was normalized either by the ablated weight or the barium signal intensity. Forty-two major and minor elements (two of them being used as internal standards) in twelve standard rocks fromt the igneous rock series of the Geological Survey of Japan were determined successfully.  相似文献   
39.
Formation of singlet charge transfer (heteroexcimer) states in the course of the fluorescence quenching of lumiflavin and riboflavin tetrabutyrate by indole and N-methylindole have been directly observed by means of time-resolved absorption spectral measurements using a picosecond laser photolysis method. Similar transient spectra have been observed also in the case of a flavoenzyme, D-amino acid oxidase.  相似文献   
40.
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