排序方式: 共有28条查询结果,搜索用时 15 毫秒
1.
The mechanisms of nitrosation of acetone through sodium enolate [CH3CO1CH2]-Na+ (1) or naked enolate [CH3CO1CH2]- (2) with methyl nitrite CH3O3NO2 (3), and the reactivity of the syn-form of 3 (syn-3) during the C-N bond formation process were investigated using ab initio molecular orbital (MO) methods. Our results have demonstrated the predominant formation of E-1-hydroxyimino-2-oxo-propane CH3COCH=NOH (4E) when the complex [CH3CO1CH2NO2(O3CH3)]-Na+ was produced kinetically via a metal-chelated pericyclic transition state (TS(CHELATED)), in which the O3 atom of syn-3 was coordinated to the Na+ atom of 1. 相似文献
2.
Yo Ueda K
ichi Mori Keiki Kouno Tokihiro Nhya 《Journal of mass spectrometry : JMS》1976,11(10):1027-1036
The mass spectra of 30 sulfinamide derivatives (RSONHR', R' alkyl or p-XC6H4) are reported. Most of the spectra had peaks attributable to thermal decomposition products. For some compounds these were identified by pyrolysis under similar conditions to be: RSO2NHR', RSO2SR, RSSR and NH2R' (in all kinds of sulfinyl amides); RSNHR' (in the case of arylsulfinyl arylamides); RSO2C6H4NH2, RSOC6H4NH2 and RSC6H4NH2 (in the case of arylsulfinyl arylamides of the type of X = H) The mass spectra of the three thermally stable compounds showed that there are several kinds of common fragment ions. The mass spectra of the thermally labile compounds had two groups of ions; (i) characteristic fragment ions of the intact molecules and (ii) the molecular ions of the thermal decomposition products. It was concluded that the sulfinamides give the following ions after electron impact: [M]+, [M ? R]+, [M ? R + H]+, [M ? SO]+, [RS]+, [NHR']+, [NHR' + H]+, [RSO]+, [RSO + H]+, [R]+, [R + H]+, [R']+ and [M ? OH]+, and that the thermal decomposition products give the following ions: [RSO2SR]+, [RSSR]+, [M ? O]+, [M + O]+ and [RSOC6H4NH2]+. 相似文献
3.
Aki H. Niiya T. Iwase Y. Goto M. Kimura T. 《Journal of Thermal Analysis and Calorimetry》2004,77(2):423-435
The formation of inclusion complexes between amoxicillin (AMPC) and 2-hydroxypropyl-β-cyclodextrin (HPCD) was investigated
by isothermal microcalorimetry and molecular dynamics simulation to evaluate the inhibitory effects on the degradation of
AMPC in aqueous solutions at various pH. The process depended significantly on the ionic species of AMPC in the solution.
In a strong acid solution, cationic AMPC and HPCD formed two different types of inclusion complexes with a 1:1 stoichiometry:
the first-type had a high association constant K
1 of 4.0-8.0·103 M-1 and included the penam ring of AMPC in the HPCD cavity (Mode I), while the second-type with a K
2 of 1.0·103 M-1 contained the phenyl group of AMPC (Mode II). Furthermore, a complex with a 1:2 (AMPC:HPCD) stoichiometry was realized in
a two-step reaction and was characterized by a smaller K
1:2of 4.0·102 M-1 and larger negative enthalpy and entropy changes than the complexes with a 1:1 stoichiometry. Since the β-lactam ring of
AMPC could be protected by inclusion with HPCD in the 1:2 complex and Mode I of 1:1 complexes, the degradation of AMPC in
the presence of HPCD was approximately four times slower than in its absence at pH 1.2 and 37°C. In weak acid and neutral
solutions, zwitterionic AMPC and HPCD formed only one type of inclusion complex with a 1:1 stoichiometry, where the phenyl
group was included (Mode II). AMPC was very stable in these solutions (t
1/2=226 h at pH=6.0) and there is little significant difference in the degradation rate between complexed AMPC and uncomplexed
AMPC. Thus, the results indicated that the inclusion complex of AMPC with HPCD, effectively increasing the stability of AMPC
in a strong acidic solution like that the stomach, would be useful for eradicating Helicobacter pylori infection and as a drug delivery system.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
4.
S Morimoto Y Hiraki I Togami M Kaji H Niiya I Joja H Yamamoto K Aono S Suzuki M Sunada 《Radioisotopes》1984,33(10):691-698
The mechanism of 201Tl chloride accumulation is unclear in thyroid gland and thyroid tumor. This report examines 108 patients that received thyroid scintigraphy examinations with both 201Tl chloride and sodium 131I. The patients were diagnosed clinically and histologically whenever possible. The ROI were obtained by subtraction imaging with both isotopes and by subtraction positive and negative areas of imaging. Dynamic curves were obtained for 201Tl chloride per square unit of each ROI. The dynamic curve in the radioiodide-accumulated area was examined. The data indicate that the clearance rate of 201Tl chloride (T15) was correlated with the sodium 131I uptake rate at 24 h (r = 0.70). 相似文献
5.
A mathematical model is presented which solves the dimensionless, transient, non-linear partial differential equations governing the competitive facilitated transport of two gases through a liquid membrane. The model incorporates the mass transfer coefficients in the boundary conditions for the free gas concentrations. Several studies were carried out. A comparison of this model with a steady-state “equilibrium core” model was excellent. Through varying the dimensionless parameters, it was found that gas I would have a higher steady-state facilitation factor than gas 2 if k1 >k2 and k-1k-2. The boundary conditions and mass transfer coefficients were also varied to see their effects on the facilitation factors. The idea of pumping one of the gases against its concentration gradient was shown to be theoretically possible. 相似文献
6.
We develop the theory of multi-polariton scattering via excitonic molecules under strong excitation. New emission lines, denoted by X- and L-bands, were observed at slightly lower energy side of two-photon Raman line in CuCl under strong excitation. In terms of the present theory, these lines can be for the first time assigned to the multi-polariton scatterings associated with the coherently (virtually) and incoherently (realy) created excitonic molecules, respectively. 相似文献
7.
We present a model which aims at describing the morphology of colonies of Proteus mirabilis and Bacillus subtilis. Our model is based on a cellular automaton which is obtained by the adequate discretisation of a diffusion-like equation, describing the migration of the bacteria, to which we have added rules simulating the consolidation process. Our basic assumption, following the findings of the group of Chuo University, is that the migration and consolidation processes are controlled by the local density of the bacteria. We show that it is possible within our model to reproduce the morphological diagrams of both bacteria species. Moreover, we model some detailed experiments done by the Chuo University group, obtaining a fine agreement. 相似文献
8.
The mechanisms of nitrosation of acetone through sodium enolate [CH3COCH2]- Na+ (1) or naked enolate [CH3COCH2]- (2) with tert-butyl nitrite (CH3)3CONO (3) were studied using ab initio molecular orbital (MO) methods. When the modified complex model was used in the elimination process, our results demonstrated the predominant formation of E-1-hydroxy-imino-2-oxo-propane CH3COCH=NOH (4E), in which a counter-cation of the base catalyst did not participate during the reaction. On the other hand, participation of the counter-cation during the reaction contributed to the formation of the Z-isomer of 4 (4Z). 相似文献
9.
Y Hiraki H Niiya Y Yamamoto M Fujishima H Yamamoto H Hayashi K Aono 《Radioisotopes》1987,36(8):409-413
The significance of high renal uptake found in patients with hematological disease who underwent bone marrow scintigraphy with 111In-chloride was investigated. In patients with a high renal uptake, the uptake in bone marrow was low, suggesting a reflection of erythropoietic activity. The reversal relationship, however, was not necessarily present. With regard to correlation with iron metabolism, significantly higher uptake of serum Fe and lower UIBC were found among those with high renal uptake, suggesting that the level of free trans ferrin in the serum is largely involved in the high uptake in the kidney. 相似文献
10.
One of the well-known convergence acceleration methods, the -algorithm is investigated from the viewpoint of the Toda molecule equation. It is shown that the error caused by the algorithm is evaluated by means of solutions for the equation. The acceleration algorithm based on the discrete Toda molecule equation is also presented.