Binding of methyl orange and its homologs by powdered nylon 66

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.     

Peculiar temperature dependence on the binding of methyl orange and its homologs by 2-hydroxyethyl methacrylate-N-vinyl-2-pyrrolidone copolymers

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.     

Peculiar temperature dependence of the binding of methyl orange and its homologs by 2-diethylaminoethyl methacrylate-N-vinyl-2-pyrrolidone copolymers

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.     

Binding of methyl orange and its homologs by polyion complexes in aqueous solution

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.     

Binding of methyl orange and its homologs by polycations containing apolar pendant groups

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.     

Thermodynamics of binding methyl orange and its homologs by polyvinylpyrrolidone: The effect of hexamethylenetetramine

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.     

Interaction of polyvinylpyrrolidone with methyl orange and its homologs in aqueous solution: Thermodynamics of the binding equilibria and their temperature dependences

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.     

Binding of butyl orange by poly(2-dimethylaminoethyl methacrylate) and copolymers of 2-dimethylaminoethyl methacrylate and N-vinyl-2-pyrrolidone: Peculiar temperature dependence of the binding

The temperature dependence of the binding of butyl orange by a homopolymer of 2-dimethylaminoethyl methacrylate (DMAEMA) and copolymers of DMAEMA and N-vinyl-2-pyrrolidone (VPy) has been examined at various pH's. The binding is very much dependent upon the temperature of the system, the pH of the binding medium, and the DMAEMA content in the polymer. In this case maximal binding is obtained at approximately 15–25° in the temperature range measured, although in most cases which have been examined, the degree of binding increases steadily with increasing temperature. This peculiar temperature dependence of the binding becomes more pronounced as the pH and the DMAEMA content are increased. The appearance of the peculiarity is discussed in terms of the pH-induced conformational changes of the polymer and the hydrophobicity of the polymer.     

Thermodynamics of binding of methyl orange and its homologs by poly(vinylpyrrolidone): The effect of inorganic electrolytes

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.     

Binding of methyl orange and its homologs by polyion complexes consisting of a piperidinium cationic polymer and various polyanions in aqueous solution

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.     

Cross-linked polyvinylpyrrolidones with increased affinity and specificity for methyl orange and its homologs

Polyvinylpyrrolidones of various degrees of cross-linkage have been prepared by radical polymerization of N-vinylpyrrolidone with methylenebisacrylamide to regulate the fraction of cross-linkage. The insoluble polymers obtained were examined for their ability to bind methyl orange and its homologs, 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 calculated. For any particular dye the extent of binding, the absolute magnitude of ΔF°, and the value of ΔS° increased as the degree of cross-linkage increased, starting with water-soluble polyvinylpyrrolidone (zero cross-linkage) and proceeding to the polymer with high cross-linking density. This behavior can be accounted for in terms of more extensive hydrophobic domains in the cross-linked polymeric matrix that enhances hydrophobic interactions in the binding process. Moreover, the cross-linked macromolecule polymerized in the presence of methyl orange and then stripped of the bound methyl orange shows substantially stronger binding for this small molecule than the polymer cross-linked in the absence of methyl orange. In contrast, the cross-linked polymer prepared similarly in the presence of the larger molecule, butyl orange, exhibits decreased affinity toward the smaller consolute, methyl orange, than either of the other polymers described. It seems, therefore, that the polymeric matrix provides favorable binding sites or pockets that can accommodate a specific small molecule. The preparative procedure, which uses a small-molecule template, molds into the polymer some structural specificity in the binding of small molecules.     

Temperature dependence on the binding of butyl orange by bovine serum albumin

The binding of 4′-dibutylaminoazobenzene-4-sulfonate anion (butyl orange) by bovine serum albumin has been examined quantitatively by an equilibrium dialysis method at 5, 10, 15, 20, 25, and 35°C. The first binding constants and the thermodynamic parameters for the formation of the first dye anion-protein complex have been calculated. The peculiar temperature dependence of the first binding constant could be observed. That is, the value of the first binding constant increases with increasing temperature until it reaches a maximum value at approximately 18°C and then decreases with raising temperature. Accordingly, this binding process is exothermic above 18°C and is endothermic below 18°C. Near 18°C the process exhibits athermal reaction. From the thermodynamic data obtained, it is evident that the favorable free energy of the binding is accompanied by an entropy gain and that the enthalpies of the binding vary from a positive (unfavorable) value below 18°C to a negative (favorable) one above 18°C. Furthermore an apparent temperature dependence of the thermodynamic functions was observed. That is, ΔF° becomes larger in absolute magnitude as the temperature increases. The positive quantity of ΔS° tends to decrease with increasing temperature. All these facts can be interpreted satisfactorily in terms of hydrophobic interactions between hydrophobic portions of the dye and nonpolar parts of the albumin.     

Binding methyl orange and hydrophobic fluorescent probes by poly(2-dimethylaminoethyl methacrylate) and copolymers of 2-dimethylaminoethyl methacrylate and N-vinyl-2-pyrrolidone: pH dependence of the binding and fluorescence intensity

The pH dependence of the interaction of poly(2-dimethylaminoethyl methacrylate) and copolymers of 2-dimethylaminoethyl methacrylate and N-vinyl-2-pyrrolidone with methyl orange, 2-p-toluidinylnaphthalene-6-sulfonate (TNS), and 1,6-diphenyl-1,3,5-hexatriene (DHT) was studied by equilibrium dialysis and fluorescence measurements at pH's 7–10. The first binding constant accompanying the binding of methyl orange and TNS by the polymers, in particular the homopolymer, shows a maximum around pH 8 and maximal fluorescence intensity of TNS is obtained around pH 8.5 in the presence of the polymers. To elucidate these observations the pH-induced conformational changes of the homopolymer were examined by potentiometric titration and viscosity measurements and the thermodynamic parameters that accompany the binding were calculated. The polymer was found to change from an extended coil at lower pH to a compact coil at higher pH. The electrostatic attraction between the sulfonate group of the small molecule and the protonated nitrogen atoms on the polymer is increased at lower pH and the hydrophobic interaction between the hydrophobic moieties of the polymer and the small molecule is enhanced at higher pH. The results obtained for the dye binding and fluorescence intensity were discussed in terms of the electrostatic and hydrophobic interactions.     

Temperature dependence on the binding of butyl orange by bovine serum albumin: The effect of urea

The effect of urea on the extent of the binding of butyl orange by bovine serum albumin has been examined by an equilibrium dialysis method. The first binding constants and the thermodynamic parameters for the formation of the first dye anion–protein complex have been calculated. Addition of urea to the binding system causes a marked decrease in the absolute magnitude of the free energy change. The enthalpy change during binding becomes more exothermic, and the entropy change tends to decrease with increasing concentration of urea. These results can be interpreted in terms of the concept that urea reduces the structure of the aqueous environment and hence lowers the tendency of apolar groups of the dye and the albumin to participate in the formation of hydrophobic interactions.     

Studies on the temperature dependence of methyl anthroate fluorescence

The temperature dependence of the fluorescence quantum hield φ_f of methyl-1-, methyl-2- and methyl-9-anthroate was investigated. For the former two esters, the trend of φ_f versus temperature is consistent with the mechanism proposed earlier to account for the temperature dependence of φ_f for meso-substituted anthracene. In this mechanism, an activated intersystem crossing to a nearby upper triplet is the only significant non-radiative decay mode. The activation energy E_A for fluorescence is a measure of the gap between the emitting singlet S₁ and the accepting triplet. Since the former state is more solvent dependent, solvents which lower the S₁ energy increase E_A and thereby increase φ_f. Thus E_A and φ_f are inversely related to the S₁ energy and directly related to each other. The situation for methyl-9-anthroate is quite different from that of the other esters. While E_A is inversely related to the S₁ energy, φ_f is not, and hence there is no correlation between E_A and φ_f. It appears that the φ_f of methyl-9-anthroate is more dependent on the nature of the solvent than on the measured E_A in that solvent. The inclusion of a temperature-independent non-radiative decay mode in the analysis does not produce results consistent with the above mechanism. It is suggested that the difference in behavior for these esters may in some way be related to an excited state geometry change which occurs for methyl-9-anthroate but not for the other two compounds.     

Interaction of poly(vinylpyrrolidone) with methyl orange and its homologs in aqueous solution over the temperature range 60–90°c

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.     

氟铌酸钾的低温固相法合成及其对甲基橙的光催化降解性能

以草酸铌、草酸钾和氟化钾为原料,采用改进的固相法在较低温度(600℃)下合成了层状K2NbO3F;测定了其对甲基橙光催化降解的催化作用,并基于紫外-可见漫反射光谱分析和X射线衍射分析初步探讨了甲基橙在自然光照条件下的光催化反应过程及降解机理.结果表明,合成的K2NbO3F与微量H2O2作用后,在自然光照条件下几乎可以使甲基橙染料完全降解;当反应温度为45℃,催化剂投加量为1g/L,H2O2用量为0.33%(体积分数)时,2h内可将初始浓度为15mg/L的甲基橙溶液几乎完全降解.就甲基橙的光催化降解机理而言,·OH自由基在其降解过程中起重要作用.