Modeling the electrophoresis of highly charged peptides: Application to oligolysines

The “coarse‐grained” bead modeling methodology, BMM, is generalized to treat electrostatics at the level of the nonlinear Poisson–Boltzmann equation. This improvement makes it more applicable to the important class of highly charged macroions and highly charged peptides in particular. In the present study, the new nonlinear Poisson–Boltzmann, NLPB‐BMM procedure is applied to the free solution electrophoretic mobility of low molecular mass oligolysines (degree of polymerization 1–8) in lithium phosphate buffer at pH 2.5. The ionic strength is varied from 0.01 to 0.10 M) and the temperature is varied from 25 to 50°C. In order to obtain quantitative agreement between modeling and experiment, a small amount of specific phosphate binding must be included in modeling. This binding is predicted to increase with increasing temperature and ionic strength.