Polymer surfactant kinetics using surface plasmon resonance spectroscopy dodecyltrimethylammonium chloride/polyacrylic acid system

Kinetics of polymer surfactant interactions and the effect of surfactant binding on the conformational dynamics of the polymer were explored in this work using surface plasmon resonance spectroscopy. Polyacrylic acid was modified with thiol to varying degrees so as to force the polymer to form different loop sizes upon adsorption on the gold SPR sensor surface. Dodecyltrimethylammonium chloride in solution was flowed over the polymer-coated sensor surface and the binding was followed in real time. It was found that control of the loop size of the polymer on the solid surface enabled in turn the control of surfactant binding, with the largest loop allowing the maximum amount of surfactant to bind and vice versa. The kinetic plot of the binding showed three distinct segments. The first segment followed convective-diffusive kinetics. The second and third segments followed first-order kinetics with the second rate being significantly faster than the first one. Careful analysis of the second segment showed that it is possible to divide it into two different segments, each following a first-order kinetics, with the second rate being slightly slower than the first one suggesting a gradual slow down of the reaction due to convolution from the polymer conformational changes. Mechanistically, the sudden increase in the rate for the third segment of surfactant binding implies that the polymer matrix is opening up so as to incorporate more surfactant molecules. This was attributed to the formation of charged double surfactant species the repulsive interaction of which prevented the polymer network from imploding. Studies using unmodified polymers suggested the possibility of sudden conformational rearrangement in the polymer network, with progress in surfactant binding. Furthermore, the reflectance of the SPR spectrum was found to increase upon surfactant binding, implying that there is a decreased efficiency of coupling of the incident radiation into the surface plasmon mode of the metal, which suggests that the surfactant actually penetrated the polymer matrix. (C) 2003 Elsevier Science (USA). All rights reserved.