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31.
The reaction process of the thermal dehydration of dilithium tetraborate trihydrate, Li2B4O73H2O, was reinvestigated from a viewpoint of reaction kinetics. On the basis of the results of thermogravimetry, constant rate thermal analysis, powder X-ray diffractometry, infrared spectroscopy and scanning electron microscopy, it was confirmed that the reaction proceeds via three consecutive kinetic steps characterized by different activation energies. The first and second kinetic steps, accompanied by the destruction of the original crystal structure of the reactant, seem to be assigned to the surface and internal reactions, respectively. During the third kinetic step, the thermal dehydration of hydrated amorphous intermediate, produced at the second kinetic step, and crystallization of the final dehydration product, Li2B4O7, are likely to take place concurrently.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
32.
Kenji Koga Kazunori Odashima 《Journal of inclusion phenomena and macrocyclic chemistry》1989,7(1):53-60
A series of water-soluble cyclophanes, made by connecting two diarylmethane units and two bridging chains via four nitrogens, were found to provide hydrophobic cavities of definite shape and size for forming inclusion complexes with various organic compounds in aqueous solution. Some chemical modifications of these cyclophanes are described.This paper is dedicated to Professor D. J. Cram to celebrate his honor in receiving the 1987 Nobel Prize in Chemistry. 相似文献
33.
Poly(phenylisopropenylketone (PPIK) and copolymers of PIK and methylmethacrylate (MMA) or styrene (St) were irradiated in benzene solution at 30° with 313 nm light (stationary irradiations) or with 347 nm light (flash photolysis experiments). Homo PPIK undergoes main chain degradation (β-scission) with ø(S) ≈ 0.05. The quantum yield for α-scission is ø(α) = 0.3. For copolymers of MMA and PIK (1 to 15 mol%), ø(S) is 0.04 independent of the copolymer composition. With copolymers of St and PIK, ø(S) was found to increase with decreasing PIK content and to approach 0.15 for very small PIK contents. The flash photolysis experiments showed: (a) the carbonyl triplet decay rate constant kT(6 × 106 sec?1) for CP-MMA-PIK samples is independent of copolymer composition but is lower than for homo PPIK (1 × 107 sec?1). In CP-St-PIK samples kT decreases with decreasing PIK content [from 8 × 106 sec?1 (12 mol% PIK) to 3 × 106 sec?1 (1 mol% PIK)]; (b) the transient spectra of triplet decay products indicate the formation of benzoyl radicals in the cases of PPIK and CP-MMA-PIK, and the formation of various different species in the case of CP-St-PIK.The results are consistent with the following concept. In homo PPIK and CP-MMA-PIK, α-scission (Norrish type I) is the dominant chemical route of triplet deactivation. In CP-St-PIK, however, type II processes become more and more important as the PIK content decreases. 相似文献
34.
Summary For the quantitative analyses of evolved CO2and H2O during the thermal decomposition of solids, calibration curves, i.e. the amounts of evolved gases vs. the corresponding
peak areas of mass chromatograms measured by TG-MS, were plotted as referenced by the reaction stoichiometry of the thermal
decomposition of sodium hydrogencarbonate NaHCO3. The accuracy and reliability of the quantitative analyses of the evolved CO2and H2O based on the calibration curves were evaluated by applying the calibration curves to the mass chromatograms for the thermal
decompositions of copper(II) and zinc carbonate hydroxides. It was indicated from the observed ratio of evolved CO2and H2O that the compositions of copper(II) and zinc carbonate hydroxides examined in this study correspond to mineral malachite,
Cu2CO3(OH)2, and hydrozincate, Zn5(CO3)2(OH)6, respectively. Reliability of the present analytical procedure was confirmed by the fairly good agreement of the mass fraction
of the evolved gases calculated from the analytical values with the total mass-loss during the thermal decompositions measured
by TG. 相似文献
35.
Fumio Yoneda Ryosuke Koga Sadao Nishigaki Shinobu Fukazawa 《Journal of heterocyclic chemistry》1982,19(4):949-951
Treatment of 6-amino-1,3-dimethyl-5-nitrosouracil (Ia) with dimethyl acetylenedicarboxylate (DMAD) in dimethylformamide (DMF) afforded 6,7-bis(dimethoxycarbonyl)-1,3-dimethyllumazine (II). Similarly, the reaction of 6-amino-1,3-dimethyl-5-phenylazouracil with DMAD gave also II. Hydrolysis of II with hydrochloric acid gave 1,3-dimethyllumazine-6-carboxylic acid (III). III was chlorinated with thionyl chloride and then aminated with ethanolic ammonia to give rise to 6-carbamoyl-1,3-dimethyllumazine (V). V was alternatively synthesized by the treatment of Ia with propiolamide in DMF. 相似文献
36.
Summary Medium-sized Gaussian basis sets are reoptimized for the ground states of the atoms from hydrogen through argon. The composition of these basis sets is (4s), (5s), and (6s) for H and He, (9s5p) and (12s7p) for the atoms Li to Ne, and (12s8p) and (12s9p) for the atoms Na to Ar. Basis sets for the2
P states of Li and Na, and the3
P states of Be and Mg are also constructed since they are useful in molecular calculations. In all cases, our energies are lower than those obtained previously with Gaussian basis sets of the same size. 相似文献
37.
T. Koga 《Theoretical chemistry accounts》2005,113(3):183-186
In many-electron atoms, the average electron momentum p represents the mean momentum of a single electron when all the electron motions are averaged. If any two electrons are considered simultaneously, however, the average momentum p splits into two different momenta, low momentum p< and high momentum p>. For the 102 atoms He through Lr in their ground states, the momenta p< and p> are systematically examined at the Hartree–Fock limit level. It is also shown that the sum p>+p< and the difference p>–p< of the two momenta constitute upper and lower bounds to the electron-pair relative momentum p12=|p1–p2| and to the electron-pair center-of-mass momentum P=|p1+p2|/2. The tightness of the bounds is discussed for the 102 atoms. 相似文献
38.
H Koga N Mori H Yamada Y Nishimura K Tokuda K Kato T Imoto 《Chemical & pharmaceutical bulletin》1992,40(4):965-970
Employing soluble denatured protein substrates and their derivatives, the proteolytic activity of rat cathepsin H was investigated. The enzyme showed aminopeptidase activity which sequentially released amino acid from the N-terminal of the substrate. The aminopeptidase activity did not act on N alpha-acetylated peptides and showed moderate ionic-strength dependence when methionyl-methylcoumarylamide was employed as a substrate. These results indicate that the activity essentially requires an N-terminal free amino group of the substrate and recognizes it electrostatically to some extent. On the other hand, the enzyme was also indicated to exhibit endopeptidase activity by employing appropriate N alpha-acetylated peptide substrates. In contrast to the aminopeptidase activity, the endopeptidase activity showed rather strict specificity, preferring hydrophobic residues at P2 and P3 sites. Because of the broad specificity and high efficiency of the aminopeptidase activity, it was difficult to directly observe endopeptidase activity in the digestion of large peptide substrates with a free alpha-amino terminal. Thus, this is the first experimental evidence that indicates endopeptidase activity by assigning internal peptide bonds cleaved by this activity. From this data, we proposed a model of the binding site of this enzyme. 相似文献
39.
Toshikatsu Koga 《Theoretical chemistry accounts》1989,75(6):417-424
Based on momentum- and position-space analyses of the moment operators for two-electron atoms, it is shown that there exists a family of two-electron wave functions which satisfy a proportionality relation, r/
1
v
/r
12
v
=p/
1
v
/p
12
v
=2–v/2, between the one and two-electron moments in position and momentum spaces, where v is an arbitrary number for which the moments are well-defined. 相似文献
40.
Tan L Yasuda N Yoshikawa N Hartner FW Eng KK Leonard WR Tsay FR Volante RP Tillyer RD 《The Journal of organic chemistry》2005,70(20):8027-8034
[Chemical reaction: See text] A Et3Al mediated intramolecular epoxide opening, cyclopropanation reaction is described. The transformation provided highly functionalized bicyclo[3.1.0]hexane systems in high efficiency and with perfect H or F endo selectivity. Application of this reaction to the synthesis of mGluR2/3 agonist 1 (43% overall yield) and a few intermediates suitable for the synthesis of other bicyclo[3.1.0]hexane mGluR2/3 agonists is discussed. 相似文献