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

Abstract

AbstractThe 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.