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Yong Jin Lim Sung Hoon Kim Hiromitsu Hamano Toru Takagishi Nobuhiko Kuroki 《Journal of polymer science. Part A, Polymer chemistry》1986,24(3):503-510
Powdered Nylon 66 was prepared as a model of amorphous polymers. The resultant powder polyamide was composed of only amorphous regions. The extent of uptake of the acid azo dyes, a homologous series of methyl orange derivatives, by the polymer was measured in an aqueous solution. The first binding constants and the thermodynamic parameters in the course of the binding were evaluated. The thermodynamic behaviors obtained are very similar to those of crosslinked polyvinylpyrrolidone. The favorable free energy of the binding is accompanied by an entropy gain and an exothermic enthalpy change. The shorter the alkyl chain of the dyes, the more negative is the enthalpy change and, hence, the smaller is the entropy change. The thermodynamic data for butyl orange showed that the binding process is athermal and is wholly an entropic effect. The binding of the dyes to the matrix is entropically favorable as a result of the operation of the hydrophobic effect. In addition, an electrostatic force is operative between the sulfonate group on the dyes and the terminal amino groups on the polyamide. 相似文献
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Toru Takagishi Yoshiro Nakata Nobuhiko Kuroki 《Journal of polymer science. Part A, Polymer chemistry》1974,12(4):807-816
The binding of methyl orange, ethyl orange, and propyl orange by polycations involving various apolar pendant groups such as methyl, ethyl, benzyl, or dodecylbenzyl groups has been examined quantitatively by an equilibrium dialysis method at 5, 15, 25, and 35°C. The first binding constants and the thermodynamic parameters in the course of the binding have been calculated. The favorable free energy of the binding is accompanied by an entropy gain and an exothermic enthalpy change. The shorter the alkyl chain of the dyes or the polymers, the more negative is the enthalpy change and hence the smaller is the entropy change. Furthermore, an increase in binding affinity can be created in the polycation upon introduction of hydrophobic groups. In particular, the binding ability of the polycation containing a dodecylbenzyl group for methyl orange is almost 300-fold that of bovine serum albumin. Therefore it is clear that hydrophobic interactions, as well as electrostatic ones, are involved in the binding. 相似文献
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Toru Takagishi Hiroshi Kozuka Nobuhiko Kuroki 《Journal of polymer science. Part A, Polymer chemistry》1981,19(12):3237-3246
Polyion complexes of sodium poly(methacrylate) and piperidinium cationic polymers [I], which are insoluble in water and have an equal number of positive and negative charges, bind organic anions (methyl orange, ethyl orange, propyl orange, butyl orange, and pentyl orange) in aqueous solution. The strength of the binding is enhanced by an increase in the hydrophobicity of the polyion complex and the small cosolute. Moreover, strong cooperative interactions appear with increased uptake of the small molecule. Urea and an inorganic electrolyte (KCl) were examined for their effect on the binding, the amount of which is strongly suppressed by these additives. The significance of hydrophobic and electrostatic interactions which accompany the binding is described. 相似文献
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Toru Takagishi Nobuhiko Kuroki 《Journal of polymer science. Part A, Polymer chemistry》1980,18(1):259-264
Hexamethylenetetramine (HMT) has been examined for its effect on the binding of methyl orange homologs, methyl orange, ethyl orange, propyl orange, and butyl orange by polyvinylpyrrolidone (PVP). In the presence of HMT the entropy changes associated with the binding tend to become more positive and the absolute magnitude in the enthalpy changes becomes smaller compared with those in the absence of HMT. These tendencies are accounted for in terms of the water-structure-promoting effect of HMT, hence the enhancement of hydrophobic interactions in the binding. PVP undergoes changes in conformation on the addition of HMT and its conformation becomes more compact. This also increases the contribution of the hydrophobic interactions to the macromolecule-small molecule interaction. Some other effects exerted by the added HMT on the binding system are also described. 相似文献
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Toru Takagishi Michihiro Shibano Yong Jin Lim 《Journal of polymer science. Part A, Polymer chemistry》1987,25(9):2585-2594
The ability of powdered Nylon 612 to bind methyl orange, ethyl orange, propyl orange, and butyl orange was investigated at 5, 15, 25 and 35°C in an aqueous solution. The amount of binding of the dye is much higher with this polyamide than with powdered Nylon 66 reported previously,1 although the former polymer has fewer amide end groups. The Van't Hoff plots of the first binding constant for the binding of butyl orange and propyl orange by powdered Nylon 612 exhibit a bell-shaped curve, whereas the plots for methyl orange and ethyl orange do not. Maximal binding occurs at approximately 15°C for propyl orange and at about 25°C for butyl orange. This is the first instance where the peculiar temperature dependence of the binding constant has been found in the binding of propyl orange, whose hydrophobicity is less than that of butyl orange. These tendencies can be accounted for in terms of increased hydrophobic of butyl orange. These tendencies can be accounted for in terms of increased hydrophobic domains in powdered Nylon 612 and enhanced hydrophobic contributions in the binding process. 相似文献
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Toru Takagishi Nobuhiko Kuroki 《Journal of polymer science. Part A, Polymer chemistry》1973,11(8):1889-1901
The interaction of polyvinylpyrrolidone with methyl orange, ethyl orange, propyl orange, and butyl orange has been studied by an equilibrium dialysis method at 5, 15, 25, and 35°C. The first binding constants and the thermodynamic parameters in the course of the binding have been calculated. It was found that the free energy and the enthalpy changes are all negative and the entropy change is largely positive. The longer the alkyl chain of the dyes, the more positive is the enthalpy change (though it is always in the negative direction) and hence the larger is the entropy change. The favorable free energy of the binding of butyl orange observed for the formation of the dye–polymer complex seems to be a result of a favorable entropy change rather than any favorable enthalpy change. Temperature dependences of the thermodynamic functions were apparently observed. That is, ΔF and ΔH become larger in absolute magnitude as the temperature increases. The positive quantity of ΔS tends to decrease with increasing temperture. All these facts obtained can be interpreted satisfactorily by the hydrophobic interaction between hydrocarbon portions of the dyes and nonpolar parts of the macromolecule. 相似文献
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Hiroshi Kozuka Toru Takagishi Hiromitsu Hamano Nobuhiko Kuroki 《Journal of polymer science. Part A, Polymer chemistry》1985,23(4):1243-1254
2-Hydroxyethyl methacrylate (HEMA)-N-vinyl-2-pyrrolidone (VPy) copolymers of various compositions have been prepared. The copolymers obtained were examined for their ability to bind a homologous series of methyl orange derivatives, methyl orange, ethyl orange, propyl orange, and butyl orange, at 5, 15, 25, and 35°C, respectively, in an aqueous solution. The first binding constants and the thermodynamic parameters that accompanied the binding were evaluated. The binding ability of the copolymer for the small cosolute was enhanced with an increase of the HEMA content in the copolymer. Moreover, a bell-shaped curve appeared in the binding of butyl orange by the copolymers having higher HEMA residues when the first binding constant was plotted as a function of temperature, whereas no such phenomenon was detected for the copolymers with less HEMA content or for the less hydrophobic dye, methyl orange, ethyl orange, or propyl orange. This peculiar temperature dependence of the first binding constant shows that the enthalpy of the binding varies from a positive (unfavorable) value below ca. 15°C to a negative (favorable) one above this temperature. This behavior can be accounted for in terms of more hydrophobic effects involved in the binding process. 相似文献
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Toru Takagishi Toshitsugu Hosokawa Minoru Okada Hiroshi Kozuka 《Journal of polymer science. Part A, Polymer chemistry》1986,24(12):3423-3431
2-Diethylaminoethyl methacrylate (DEAEMA)–N-vinyl-2-pyrrolidone (VPy) copolymers of various compositions have been synthesized. The resultant copolymers were examined for their ability to bind methyl orange and its homologs, in particular butyl orange, at 5, 15, 25, and 35°C in aqueous solutions. The amount of binding of butyl orange is much higher with the copolymers than with polyvinylpyrrolidone or with 2-hydroxyethyl methacrylate–N-vinyl-2-pyrrolidone copolymers. Introduction of only 3% of the hydrophobic DEAEMA residue increases markedly the binding affinity toward the cosolute. Maximal binding is obtained at 15°C in the temperature range measured. This peculiar temperature dependence of the extent of binding is explicable on the basis of hydrophobic effects involved in this binding. The peculiar temperature dependence disappeared in aqueous solution of NaSCN which acts as a water-structure breaker: the extent of binding changes regularly with temperature. This is interpretable only in terms of reduction of hydrophobic contribution to the binding. With propyl orange, which is a less hydrophobic cosolute than butyl orange, the peculiarity of the binding was not detected. 相似文献
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Toru Takagishi Koichi Imajo Kimio Nakagami Nobuhiko Kuroki 《Journal of polymer science. Part A, Polymer chemistry》1977,15(1):31-38
The extent of binding of methyl orange, ethyl orange, propyl orange, and butyl orange by poly(vinylpyrrolidone) has been measured in aqueous solutions of inorganic electrolytes such as NaCl, LiCl, NaSCN, and NaClO4 by an equilibrium dialysis method. The effect of the salts on the first binding constants and the thermodynamic functions which are accompanied by the dye—polymer association process was investigated relative to the corresponding values in the absence of such salts. It was found that in aqueous solutions of NaCl and LiCl the enthalpy change accompanying the binding is small and the largest contribution to the free energy of binding is from the positive entropy gain. For NaSCN and NaClO4, the values of ΔF° and ΔH° were both large and negative and the value of ΔS° was small and negative. Thus, the favorable free energy for the complex formation was due entirely to the negative enthalpy term. These characteristics of the thermodynamic quantities are discussed in terms of changes in structural properties of water in the vicinity of the binding entities and conformational changes of the polymer to which the dye is bound due to the added foreign electrolytes. 相似文献
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Toru Takagishi Hiroshi Kozuka Nobuhiko Kuroki 《Journal of polymer science. Part A, Polymer chemistry》1983,21(2):447-455
A study was made of the formation of polyion complexes between a piperidinium cationic polymer and polyanions and of the binding of azo-dye anions (methyl, ethyl, propyl, and butyl orange) by these complexes. Sodium poly(acrylate), poly(styrenesulfonate), dextran sulfate, and carboxy-methylcellulose were used as polyanions. The resultant polyion complexes (insoluble in aqueous solutions) were compared for their ability to bind the small organic molecules in aqueous solutions, for example, of urea and an inorganic electrolyte (KCI), and exhibited a strong binding affinity toward these small anions. Polyion complexes that consisted of sodium poly(acrylate), dextran sulfate, and carboxymethylcellulose as polyanions cooperated in the binding, whereas the polyion complex of sodium poly(styrenesulfonate) did not. It was suggested that small organic anions interact with the polyion complexes primarily through electrostatic and hydrophobic forces. 相似文献
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A method for the synthesis of benzo[b]selenophenes was perfected. 3-Oxo-2,3-dihydrobenzo[b]selenophene and 2-methyl-3-oxo-2,3-dihydrobenzo[b]selenophene exist only in the keto form. 3-Methylbenzo[b]selenophene was obtained by the reaction of 3-oxo-2,3-dihydrobenzo[b]selenophene with methylmagnesium iodide. Metallation of benzo[b]selenophene with butyllithium proceeds at the 2 position of the selenophene ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1475–1480, November, 1970. 相似文献
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Toru Takagishi Young Joo Kim Toshitsugu Hosokawa Keiji Morimoto Kenji Kono 《Journal of polymer science. Part A, Polymer chemistry》1993,31(2):365-371
The copolymers of methyl quaternized 2-dimethylaminoethyl acrylate and styrene, 2-vinyl naphthalene, acrylic acid iso-octyl ester, or acrylic acid n-butyl ester have been prepared. Studies were made of the binding of a “binding probe,” methyl orange, by the copolymers in aqueous solution. The first binding constants and the thermodynamic parameters in the course of the binding were evaluated. Furthermore, the intensity of fluorescence of a hydrophobic fluorescent probe, 2-p-toluidinylnaphthalene-6-sulfonate, in the presence of these polymers was investigated. In addition, the fluorescence spectra of monomer and excimer emissions of the polymers with aromatic residues were measured. The excimer/monomer fluorescence intensity ratio was studied in the presence of various additives such as methyl orange, urea, methanol, and NaCl to gain an insight into the nature of microdomains in the polymer. The nature and phenomena of dye binding and hydrophobic fluorescent probe binding with the polymers are discussed. © 1993 John Wiley & Sons, Inc. 相似文献
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首先以对三联苯(TP)和对苯二甲酰氯(TC)为单体合成了酮基聚合物前体(TP-TC),而后基于席夫碱反应将三聚氰胺(MA)与之交联得到胺功能化的多孔有机聚合物TP-TC-MA。通过扫描电镜(SEM)、透射电镜(TEM)、傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)、氮气吸附-脱附(BET)以及零电荷点(pHpzc)的测定等手段对合成的多孔有机聚合物进行表征。以染料废水中典型的阴离子染料甲基橙为研究对象,研究了TP-TC-MA对其吸附行为,并探讨了吸附机制。利用紫外-可见分光光度计(UV-Vis)得出目标污染物的紫外吸收光谱标准曲线,标准曲线拟合相关系数(R2)为0.999。结果表明,TP-TC-MA由于具有高比表面积(708.5 m2/g)和总孔体积(0.556 cm3/g)以及丰富的含氮基团,对阴离子染料甲基橙表现出优异的吸附性能。TP-TC-MA对水中甲基橙的吸附动力学符合准二级动力学方程,吸附平衡数据可以采用Langmuir等温吸附模型描述。经由Langmuir等温吸附模型计算得到的理论最大吸附容量为156.3 mg/g。选择性实验结果表明,TP-TC-MA对阴离子染料甲基橙具有更强的吸附作用,吸附作用机理可归结为静电相互作用、氢键和π-π相互作用等。在重复使用5次之后,TP-TC-MA对甲基橙仍保持90%以上的去除率,表明材料具有良好的稳定性和重复利用性,在染料废水处理中具有很好的应用前景。 相似文献
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Toru Takagishi Kimio Nakagami Koichi Imajo Nobuhiko Kuroki 《Journal of polymer science. Part A, Polymer chemistry》1976,14(4):923-929
The binding of methyl orange, ethyl orange, propyl orange, and butyl orange by poly(vinylpyrrolidone) has been examined by a technique of equilibrium dialysis over a high temperature range (60–90°C). The first binding constants and the thermodynamic parameters in the course of the binding were evaluated. The results obtained at these temperatures were compared to those at lower ones (5–35°C) described previously in order to estimate the contribution of hydrophobic bonds to the binding. It was found that at the 60–90°C range complex formation between the dye and the macromolecule is associated with an exothermic enthalpy change and a positive entropy change. The enthalpy and entropy changes of the binding are of the order of ?4.5 kcal/mole and 6 eu, respectively, for each dye measured. Thus the binding is mainly enthalpy-controlled. Furthermore the effect of the alkyl chain length of the dye on both the ΔH° and ΔS° values is not pronounced. Also temperature dependences of the ΔH° and ΔS° terms were not observed. All these observations in the higher temperature range can be explained as a result of the disruption of water structure in the binding environment and hence a decrease in hydrophobic bond formation between the dye and the polymer. 相似文献
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Toru Takagishi Toshihiko Ueno Nobuhiko Kuroki Shoji Shima Heiichi Sakai 《Journal of polymer science. Part A, Polymer chemistry》1984,22(6):1281-1289
The interaction of α-poly-L -lysine and ε-poly-L -lysine with methyl and ethyl orange was studied by equilibrium dialysis and spectroscopic methods. The results of the dialysis measurements indicated that the extent of binding by ε-polypeptide is substantially higher than that by α-polypeptide, despite the much greater molecular weight of the latter. This difference in binding affinity was interpreted in terms of the increased conformational adaptability of ε-polypeptide because of its highly flexible structure. Furthermore, ε-polypeptide exhibited strong cooperative binding. In addition, the effect of the successive addition of α- and ε-polypeptides on the absorption spectra of methyl and ethyl orange was investigated. The addition of α-polypeptide with a molecular weight of 400,000 produced a new absorption peak at a shorter wavelength, due to the stacked dye molecules on the polypeptide chain, whereas that of ε-polypeptide did not. From the results of spectroscopic measurements a possible mode of interaction between these two polypeptides and the small molecule is discussed. 相似文献