The direct analysis of sedimentation equilibrium results obtained with polymerizing systems

Abstract

Theory is presented in relation to sedimentation equilibrium results obtained with polymerizing systems, which permits evaluation of the activity of the monomer as a function of total weight concentration. In contrast to established methods, the suggested procedure does not involve the solution of simultaneous equations which are sums of exponentials or the determination of weight-average molecular weights. A major advantage of the method is that it avoids errors inherent in differentiation and integration steps. An extrapolation to infinite dilution is involved, but this is to a defined limit and is uncomplicated by the existence of critical points in the relevant plot. The method is capable of detecting possible volume changes inherent on polymer formation, of treating systems where activity coefficients of solute species are functions of total concentration and of describing the system in terms of relevant equilibrium constants. These points and comparisons with existing methods of analysis are illustrated with numerical examples and with results obtained with lysozyme at pH 6.7. The lysozyme results are interpretable in terms of either a non-ideal monomer-dimer system or a monomer-dimer-trimer system