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.     

Amphiphilic copolymers with increased affinity for substrates

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.     

Binding of methyl orange and the hydrophobic fluorescent probe, 2-p-toluidinylnaphthalene-6-sulfonate,by 2-dialkylaminoethyl methacrylate-N-vinyl-2-pyrrolidone and related copolymers

The copolymers of N-vinyl-2-pyrrolidone and 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-dimethylaminoethyl acrylate, or 2-dimethylaminopropyl acrylamide 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 accompanying 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. The nature and phenomena of dye binding and hydrophobic fluorescent probe binding with the polymers are discussed.     

Binding of methyl orange and its homologs by powdered nylon 612: Peculiar temperature dependence on the binding

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.     

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.     

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.     

A screened indicator of methyl orange with sulfonated copper phthalocyanine

Summary Copper phthalocyanine tetra sulfonate pottasium salt, has been found to be very useful as a screening-dye to improve methyl orange end-points.Mixtures of methyl orange and dye in varying proportions have been prepared and tested for their indicator-action. The transformation interval of the indicator is found to change as the concentration of the dye is varied in the mixture.The optimum concentration of the dye to be used with a certain amount of methyl orange is determined so as to give a mixed-indicator that functions most satisfactorily in all titrations where methyl orange is used.     

Microwave-assisted sol–gel synthesis for molecular imprinting

Molecularly imprinted polymers have been the subject of intense research for several decades in both academic and industrial settings. In this paper, we introduce a novel microwave-assisted sol–gel method for molecular imprinting of silica microspheres. The microspheres were characterized, and their adsorption of imprint and non-imprint molecules was investigated. The dye molecules methyl orange and ethyl orange were used as templates. Good molecular imprinting was observed as evaluated by the re-adsorption of dye into the silica matrix followed by the removal of dye from the supernatant solution.     

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.     

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.     

Interaction of Crystal Violet and Polyanions in Aqueous Solution

The effect of several polyelectrolytes on the absorption spectrum of crystal violet (CV) has been studied over a wide range of pH. The following polymers were used: isotactic poly(methacrylic acid), PMA_i; conventional poly(methacrylic acid), PMA_c; a methacrylic acid (80%)-styrene (20%) copolymer, PMAS; and poly(styrene sulfonic acid), PSSA. Distinctly different effects were observed in the four cases. This has been interpreted in terms of a dependence of the degree and mode of binding of cationic dye molecules onto the polyacids on the hydrophobicity of the macroions.     

Binding of anthraquinone dyes by polyion complexes consisting of a piperidinium cationic polymer and various polyanions in aqueous solution

The extent of binding of 1-amino-4-alkylaminoanthraquinone-2-sulfonates (alkyl?methyl, ethyl, propyl, and butyl), which have different chemical structures from methyl orange derivatives, by polyion complexes consisting of a piperidinium cationic polymer and various polyanions such as sodium poly acrylate, poly methacrylate, poly styrenesulfonate, carboxymethylcellulose, and dextran sulfate, was measured in an aqueous solution. The effect of alkyl group of the anthraquinone dye on the binding behavior was investigated. Also, the resultant binding characteristics were compared with those previously observed with methyl orange and its homologs. These polyion complexes exhibited very strong binding affinity toward the anthraquinone dye. The polyion complex of the polycation and sodium poly styrenesulfonate bound the dye noncooperatively and the binding process was athermal. The first binding constant accompanying the binding is of the order of 10⁵–10⁶. In contrast, the polyion complexes composed of the polycation and the other polyanions exhibited strong cooperative binding and the binding process was exothermic. The possible mode of binding is discussed.     

疏水相互作用对阳离子聚电解质与染料键合的影响

用平衡渗析法研究了阳离子聚电解质PAm·MG 和P(St-Am·MG)与甲基橙(MO)及P(St-Am·MG)与MO的同系物乙基橙(EO)、橙武Ⅳ(O-Ⅳ)在25、35、45和55 ℃下相互作用的热力学. 由K1otz方程, 求得键合常数K_1和热力学参数ΔG、ΔH及ΔS. 含疏水基的P(St-Am·MG)与MO的键合能力比不含疏水基的PAm·MG 强. P(St-Am·MG)与不同染料作用时, 键合程度为O-Ⅳ>EO>MO, 即染料的疏水性越强, 与高聚物的作用程度越大.键合体系加入脲或甲醇, 疏水相互作用受到破坏, 导致高聚物与染料之间的键合受到削弱.     

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.     

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.     

Interactions of water-soluble polymers with small molecules II: Poly(2-diethylaminoethyl methacrylate)-methyl orange and its homolog systems at different temperatures

In order to investigate the interactions of poly(2-diethylaminoethyl methacrylate) (PDEAEMA) with methyl orange and its homologs in solution, temperature dependence of the complex formation has been examined in detail by the measurements of transmittance and specific conductance for the systems. Furthermore, the binding course of dyes to PDEAEMA has been studied on the basis of thermodynamic parameters obtained from equilibrium dialysis experiments at different temperatures. It was observed that the flocculation process shifted to lower dye concentrations in accordance with increasing hydrophobicity of the dyes in the order, methyl orange < ethyl orange < butyl orange, and the process of complex formation was characterized by three separate regions according to the slope of specific conductivity-mixing ratio curve for mixtures of PDEAEMA and dye. The temperature dependences of F,H and S suggest that, for dyes-PDEAEMA complex formation, the hydrophobic interaction is predominant at a low temperature but the electrostatic interaction becomes important as the temperature increases.     

Aggregation and protein binding of sodium maleate copolymers with varying hydrophobicities

Copolymers of sodium maleate with methyl methacrylate, styrene, or vinyl acetate have been synthesized and studied in aqueous NaCl solutions of various ionic strengths. The polymers are polyelectrolytes with varying hydrophobicities, and their solution properties have been studied using static and dynamic light scattering. Copolymers containing methyl methacrylate or styrene were shown to aggregate in water upon increasing salt concentration. Copolymers of sodium maleate and vinyl acetate do not associate with increasing ionic strength. The binding of bovine serum albumin and cytochrome C to the sodium maleate copolymers was also investigated by light scattering. It was observed that cytochrome C forms complexes with the copolymers containing methyl methacrylate or vinyl acetate whereas albumin does not bind to any of the copolymers studied. Copyright © 2004 John Wiley & Sons, Ltd.     

Interaction of crosslinked polyethylenimine with a homologous series of methyl orange derivatives in aqueous solution

Polyethylenimine (PEI) was crosslinked with dichloroethane, glyoxal, or glutaraldehyde and polymers of various degrees of crosslinkage were made. The insoluble polymers obtained were examined for their ability to bind methyl orange and its homologs, methyl, ethyl, propyl, and butyl orange at 5, 15, 25, and 35°C, respectively, in an aqueous solution. PEI crosslinked with glutaraldehyde showed markedly increased binding affinity toward these cosolutes compared with the polymers crosslinked with dichloroethane or glyoxal. The extent of the binding increased with an increase in the degree of crosslinkage. These results suggest that the enhancement of the binding by the crosslinking is due mainly to a dual effect, introduction of hydrophobic moieties and proximity of neighboring polymer chains. The first binding constants and the thermodynamic parameters that accompanied the binding were calculated. The thermodynamic data show that the binding process is athermal and is stabilized entirely by the entropy term. Water-soluble PEI exhibited stronger cooperative interactions than the crosslinked polymer because the mobilities of the chains of the former are greater than those of the latter.     

Interaction of an anticancer drug,methotrexate with amphiphilic copolymers of methyl quaternized 2-dimethylaminopropyl acrylamide and styrene

The copolymers of methyl quaternized 2-dimethylaminopropyl acrylamide and styrene have been prepared. Studies were made of the binding of an anticancer drug, methotrexate by the copolymers, bovine serum albumin, and polyvinylpyrrolidone in aqueous solution. The first binding constants and the thermodynamic parameters in the course of the binding were evaluated and compared with those of a binding probe, methyl orange and its homologs in order to gain insight into the nature of drug binding and to apply the drug-polymer complex to a drug-delivery system. The nature and phenomena of drug binding with the polymers are discussed.     

Exploiting stored TiO2 electrons for multi-electron reduction of an azo dye methyl orange in aqueous suspension

The mechanism of multi-electron reduction of methyl orange (MO) azo dye on TiO₂ nanoparticles has been studied performing stopped flow technique. A multi-electron reduction of azo dye has been investigated. It was found that a multistep reduction of the dye takes place: the stored electrons reduce the conjugative system of the azo group resulting in the decolorization of the dye and leading to the formation of hydrazine derivative followed by further 2 electron transfer step leading to the cleavage of the N–N bond and the formation of aromatic amines. The FTIR analysis of the products confirms the proposed mechanism of the dye reduction. The kinetic parameters and of the multi-electrons reduction of the MO have been determined. The rate of MO reduction was found to be dependent on both the TiO₂ electrons and the dye concentrations.