Theoretical Basis of Macromolecular Chromatography

Abstract

Some of the unique chromatographic characteristics which materialize as molecular size increases to very large values are discussed. The basic theory of chromatography apparently remains intact, but the enormous energy range, the reduced diffusion, and the approach to a continuum in molecular size and properties lead to distinct features and problems. These are explored from thermodynamic, dynamic, and methodology viewpoints. The equations most pertinent to the subject are given and their applications explained. These deal with resolution, column efficiency, speed, gradients, and the maximum of resolvable peaks. We conclude that separation does not occur so spontaneously with macromolecules as with smaller molecules; but, with proper optimization, extremely slight relative differences in molecular structure and composition are adequate for separation.