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11.
Summary In the aqueous solutions of poly(N-vinylacetamide) in the presence of Na2SO4 or (NH4)2SO4, the intrinsic viscosities were small and the Huggins constants were large compared with those in water. Similar but much
less effects were observed for NaF. Opposite effects were found, however, for NaSCN. The poor solvent quality of aqueous sulfate
solutions was significantly improved by the addition of guanidine hydrochloride to 3 M or higher. Urea was much less effective
in improving the solvent quality. The different M28.8neffects observed between urea and GdnHCl may be explained by their different
binding affinities to amide group. Solubilization of PNVA flocculates induced by the presence of 0.8 M Na2SO4 took place by adding urea to 1 M, although only small changes were detected in the viscosity behavior accompanying the addition
of 1 M urea.
Received: 12 June 1997 Accepted: 4 August 1997 相似文献
12.
Motohiko Hikuma Haruo Obana Takeo Yasuda Isao Karube Shuichi Suzuki 《Analytica chimica acta》1980,116(1):61-67
The sensor consists of immobilized E. coli (which contains glutamate decarboxylase) and a carbon dioxide gas-sensor. Continuous introduction of sample solution into a flow system incorporating the sensor gives a potential which increases until a steady state is reached after 5 min. Measurements can also be made with only a 1- or 3-min introduction period with little loss of sensitivity. Calibration plots of mV measurements vs. logarithmic glutamic acid concentration are linear in the range 100–800 mg l-1. The sensor is highly selective, stable and reproducible. It has been applied to the determination of glutamic acid in fermentation broths. 相似文献
13.
14.
The number of perfect rnatchings for the linear 2 × 2 ×n cubic lattice was analytically derived by diagonalizing the skew—symmetric 4n × 4n determinant, whose non—zero off—diagonal elements are either ±1 or ±i (pure imaginary number). The basic formulation invoking the matrix manipulation follows that of Kasteleyn, but the result obtained in this paper is the first example of the analytical solution for a special case of the three-dimensional Ising model.received by the Publisher 20 September 1989 相似文献
15.
16.
Funyu S Isobe T Takagi S Tryk DA Inoue H 《Journal of the American Chemical Society》2003,125(19):5734-5740
Visible light irradiation of a reaction mixture of carbonyl-coordinated tetra(2,4,6-trimethyl)phenylporphyrinatoruthenium(II) (Ru(II)TMP(CO)) as a photosensitizer, hexachloroplatinate(IV) as an electron acceptor, and an alkene in alkaline aqueous acetonitrile induces selective epoxidation of the alkene with high quantum yield (Phi = 0.6, selectivity = 94.4% for cyclohexene and Phi = 0.4, selectivity = 99.7% for norbornene) under degassed conditions. The oxygen atom of the epoxide was confirmed to come from a water molecule by an experiment with H(2)(18)O. cis-Stilbene was converted into its epoxide, cis-stilbeneoxide, without forming trans-stilbeneoxide. trans-Stilbene, however, did not exhibit any reactivity. Under neutral conditions, an efficient buildup of the cation radical of Ru(II)TMP(CO) was observed at the early stage of the photoreaction, while an addition of hydroxide ion caused a rapid reaction with the cation radical to promote the reaction with reversion to the starting Ru(II)TMP(CO). A possible involvement of a higher oxidized state of Ru such as Ru(IV), Ru(V), Ru(VI) through a dismutation of the Ru(III) species was excluded by an experiment with Ru(VI)TMP(O)(2). Decarbonylation of the Ru complex was also proven to be invalid. A reaction mechanism involving an electron transfer from the excited triplet state of Ru(II)TMP(CO) to hexachloroplatinate(IV) and subsequent formation of OH(-)-coordinated Ru(III) species, leading to an oxo-ruthenium complex as the key intermediate of the photochemical epoxidation, was postulated. 相似文献
17.
Sakae Uemura Haruo Miyoshi Masaya Okano Isao Morishima Toshiro Inubushi 《Journal of organometallic chemistry》1979,165(1):9-19
Treatment of norbornene, norbornadiene, benzonorbornadiene, and chloro- and methoxy-benzonorbornadiene with thallium(III) acetate in methanol affords only the corresponding cis-exo-acetoxythallation adducts in a sharp contrast to oxymercuration of such strained olefins where methoxymercuration prevails. In the cases of substituted benzonorbornadienes the products are obtained as the regioisomeric mixtures, the isomer ratio being determined by 13C NMR. In the cases of 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2-methyl-2,3-dicarboxylic anhydride, and 5-norbornen-2-endo-carboxylic acid, lactonization occurs to give a trans-oxythallation adduct having a lactone ring, no introduction of either methoxy or acetoxy groups being observed. 1H and/or 13C NMR data for several new oxythallation adducts are provided. The alkaline sodium borohydride reduction of adducts in methanol affords mainly the parent olefin together with 10–16% yields of the corresponding exo-alcohol. 相似文献
18.
Poly(gamma-glutamic acid) (gamma-PGA) is a biosynthetic polymer, and the carboxyl groups are able to undergo a chemical modification. In this study, poly(alpha-propyl gamma-glutamate) (gamma-PGA propylate) was synthesized by the esterification of these carboxyl groups to yield a thermosensitive and biodegradable polymer. In aqueous solution, the gamma-PGA propylate can impart thermosensitivity by controlling the hydrophobic-hydrophilic balance of the gamma-PGA polymeric chains. 相似文献
19.
Toshio Takido Sachiko Tamura Kenji Sato Haruo Kamijo Toshikatsu Nakazawa Manabu Seno Tadashi Hata 《Journal of heterocyclic chemistry》1998,35(2):437-443
The synthesis of hexahydrooxoepithiopyridinedicarboxyimide (5: X2 = N-Ph) by the reaction of thioamides 1 with N-substituted maleimide ( 2a ) was examined. The reaction of primary thioamides, such as thiobenzamide and p-toluthioamide with N-phenylmaleimide gives compounds 5 together with corresponding 4-hydroxy-1,3-thiazoles 4 . However, a similar reaction of secondary thioamides, such as N-methylthioacetamide, thiobenzanilide, with N-phenylmaleimide did not provide compounds 5 without addition of acid. The reaction pathway and the configuration of 5 were also investigated. 相似文献
20.
Akira Nishinaga Toshio Itahara Tadashi Shimizu Haruo Tomita Kanji Nishizawa Teruo Matsuura 《Photochemistry and photobiology》1978,28(4-5):687-692
Abstract— The mechanisms by which 4-substituted 2,6-di- t -butylphenols are oxygenated by base- and Co(II) Schiff base complex-catalysis into o - or p -peroxyquinols and their Co(III) complexes, respectively, have been investigated. For the base-catalyzed oxygenation, a one-step ionic mechanism involving no radical species is suggested to be the most probable one. For the formation of the peroxycobalt(III) complexes, the following stoichiometry is concluded: ArOH + Co(II) + 5/4 O2 → peroxycobalt(III) complex + 1/2 H2 O. A mechanism involving an electron transfer between the phenols and the Co(II)-O2 complex followed by further electron transfer between the formed phenoxy radicals and the Co(II) complex to give the corresponding phenolate anions is proposed. 相似文献