Off-campus UMass Amherst users: To download dissertations, please use the following link to log into our proxy server with your UMass Amherst user name and password.

Non-UMass Amherst users, please click the view more button below to purchase a copy of this dissertation from Proquest.

(Some titles may also be available free of charge in our Open Access Dissertation Collection, so please check there first.)

Capillary electrophoresis of polyelectrolytes in dilute neutral polymer solutions: Simulations and model experiments

Margaret Ellen Starkweather, University of Massachusetts Amherst


The electrophoretic separation of polyelectrolytes in dilute neutral polymer solutions are investigated through computer simulations and capillary electrophoresis experiments. The isolated entanglement dynamics of a mobile "probe" polyelectrolyte and "host" neutral polymer are simulated, using a Monte Carlo algorithm, providing insight into the effect of various probe and host parameters on molecular weight discrimination. Experiments employing narrow dispersity molecular weight fractions of pullulan as model most and poly(styrene sulfonate) as model probe, are used for investigation of bulk separation trends, in particular, to assess the role of host molecular weight. Both simulation and experiments indicate that probe separation in dilute matrices is dominated by the duration of probe/host entanglements. Single probe/host pairs alone are shown to impart a strong molecular weight discrimination, and this discrimination is highly affected by the size of the matrix polymer. A plot of probe mobility versus log of molecular weight is sigmoidal with the "best" separation occurring at comparable probe and host molecular weights. Probe separations are noted at concentrations as low as c*/8. A new understanding of the underlying molecular mechanisms of separation in dilute polymer solution matrices is achieved.

Subject Area


Recommended Citation

Starkweather, Margaret Ellen, "Capillary electrophoresis of polyelectrolytes in dilute neutral polymer solutions: Simulations and model experiments" (1998). Doctoral Dissertations Available from Proquest. AAI9841924.