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排序方式: 共有191条查询结果,搜索用时 15 毫秒
1.
T. Obara T. Iijima J. Komiyama S. Ikeda H. Ishikawa T. Nakagawa 《Journal of polymer science. Part A, Polymer chemistry》1978,16(9):2393-2402
From the analysis of the permeation of 35S labeled ethanesulfonic acid, through nylon-6 films sorption isotherms were obtained. The films are characterized by their largely different content of carboxyl and amino end groups. It was found that the shape of the isotherm depends on the molar ratio of the two end groups: an S-shape curve for the film containing the carboxyl end group larger than the amino end group and a Langmuir-type curve for the film containing comparable numbers of end groups. These results were explained by the McGregor-Harris theory in which the acid dissociation constants of the two end groups in nylon were estimated experimentally. 相似文献
2.
Takarada T Yashiro M Komiyama M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(21):3906-3913
Oligopeptides are efficiently hydrolyzed by Ce(IV) to the corresponding amino acids under mild conditions. The pseudo first-order rate constants for the hydrolysis of H-Gly-Phe-OH and H-Gly-Gly-OH at pH 7.0 and 50 degrees C are 3.5 x 10(-1) and 2.8 x 10(-1) h(-1), with [Ce(NH4)2(NO3)6]0=10mM (the half-lives are 2.0 and 2.5 h). The catalytic activity of the Ce(IV) is far greater than those of other lanthanide ions and non-lanthanide ions. No oxidative cleavage was observed under the reaction conditions. Catalytic turnover of the Ce(IV) was also evidenced. The hydrolysis is fast especially when the substrates have no metal-coordinating side chains. Tripeptides and tetrapeptides are hydrolyzed at the similar rates as the dipeptides. In the hydrolysis of tripeptides, the amide linkage near the N-terminus is preferentially hydrolyzed. Neither the N-carbobenzyloxy derivative nor the amide of H-Gly-Phe-OH is hydrolyzed to a measurable extent, showing that both the terminal amino group and the carboxylate are coordinated to the Ce(IV) ion. This complexation is further confirmed by 1H NMR spectroscopy. The Ce(IV) ion is therefore one of the most active catalysts for peptide hydrolysis. 相似文献
3.
Treatment of acetonide protected 4,5-dihydroxy-2-chloroglycidic ester or its rearrangement product, the acetonide protected 4,5-dihydroxy-3-chloro-2-oxo ester, with magnesium halides gave 4-halo-3-hydroxy-2-pyrone in excellent to reasonable yields in one pot. The mechanism of this novel one pot rearrangement-cyclization reaction is also proposed. 相似文献
4.
Hiroyuki Asanuma Sumie Gotoh Takeshi Ban Makoto Komiyama 《Journal of inclusion phenomena and macrocyclic chemistry》1997,27(3):259-264
Poly(2-vinyl-4,6-diamino-1,3,5-triazine) efficiently binds nucleic acid bases and nucleosides in water by using complementary hydrogen bonding. The binding activity decreases in the order: U, T > A C, G. The corresponding monomer shows virtually no activity, indicating a predominant role of polymer effect for the molecular recognition in water. 相似文献
5.
The conductance of potassium iodide has been measured in the solvents ethylene carbonate, water, methyl ethyl ketone, and pairwise mixtures of these solvents at 40°C; and ethylene carbonate-water, tetramethylene sulfone-water, dimethyl sulfoxide-water, tetrahydrofuran-water, ethylene carbonate-tetramethylene sulfone-water, ethylene carbonate-tetramethylene sulfone, and tetrahydrofuran-dimethyl sulfoxide at 25°C. For dielectric constants greater than about 60, the pairing constants KA are in the range 0.3–2.0; no correlation between KA and solvent properties could be established. For lower dielectric constants, KA increases exponentially with decreasing dielectric constant. Addition of a proton, acceptor to water initially decreases KA regardless of whether the dielectric constant of the mixture is higher or lower than that of water, suggesting that ion pairs in water may be stabilized by cage structures. The Walden product Ao is also decreased by the addition of proton acceptors. 相似文献
6.
Homogeneous solutions are formed from equimolar amounts of Ce(NH4)2(NO3)6 and EDTA. These solutions hydrolyze single-stranded DNA far more efficiently than double-stranded DNA. In contrast, Ce(IV) hydroxide gel, obtained in the absence of EDTA, hydrolyzes both single-stranded and double-stranded DNAs at almost the same rates. In order to achieve this substrate-specificity sufficiently, the mole ratio of EDTA to Ce(NH4)2(NO3)6 must be 1.0 or greater. By using this remarkable specificity of Ce(IV)/EDTA complex, gap-site in substrate DNA is selectively hydrolyzed. The scission-site is modulated by use of appropriate combination of oligonucleotide additives. The reactions have been kinetically analyzed. 相似文献
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9.
Hidefumi Hirai Makoto Komiyama 《Journal of polymer science. Part A, Polymer chemistry》1975,13(11):2419-2435
The alternating copolymerization of methyl methacrylate with styrene in the presence of stannic chloride at ?50°C in toluene was kinetically investigated both under photoirradiation and with the tri-n-butylboron-benzoyl peroxide initiator. The concentrations of the binary and ternary molecular complexes in the copolymerization solution were estimated by use of the equilibrium constants. The rates are found to be proportional to the 1.5th and 1.0th orders of the concentration of the ternary molecular complex composed of stannic chloride, methyl methacrylate, and styrene, under photoirradiation and with initiator, respectively. The conversion increases proportionally with the polymerization time, while the degree of polymerization is constant irrespective of the time. The rates depend linearly upon the square root of the intensity of the incident light and upon the concentration of tri-n-butylboron, respectively. The alternating copolymerization is confirmed experimentally to precede the homopolymerization of the monomer charged in large excess both under photoirradiation and with initiator. The kinetic results indicate consistently that the alternating copolymerization proceeds through the homopolymerization of the ternary molecular complex in the steady state with a bimolecular termination. Both the conventional radical mechanism and the double complex mechanism are unsuitable for the present alternating copolymerization. 相似文献
10.
Liang X Asanuma H Kashida H Takasu A Sakamoto T Kawai G Komiyama M 《Journal of the American Chemical Society》2003,125(52):16408-16415
Two diastereomers of a photoresponsive oligodeoxyribonucleotide tethering a trans-azobenzene, based on the chirality of the central carbon of a diol linker, were separated by reversed-phase HPLC. On the basis of 2D NMR analysis, absolute configurations of the diastereomers alpha and beta (tentatively designated from differences in their retention time) were determined as R- and S-forms, respectively. For both diastereomers, their NMR-determined duplex structure showed that trans-azobenzene intercalates between base pairs, because distinct NOEs were observed between the protons of azobenzene and those of the adjacent base pairs, such as with the imino protons and methyl protons of thymine. The melting temperatures of both duplexes were higher than that of the corresponding native duplex, which contained no azobenzene residue, due to the intercalated trans-azobenzene stabilizing the duplex by a stacking interaction. Between these two diastereomers, differences in T(m) were also found: the melting temperature of the R-form duplex (alpha-isomer) was higher than that of the S-form (beta-isomer). On the basis of the NMR-determined structure, this difference was attributed to the fact that the S-form (beta isomer) causes more stress forming the duplex than does the R-form (alpha isomer) due to disturbances of the right-hand helix. 相似文献