| Abstract: | Dilute solutions of rigid helical macromolecules with permanent dipole moments have been studied with dielectrophoresis. The polymers used were poly-γ-benzyl-L -glutmate and poly-n-butyl isocyanate, both fractions of average molecular weight 120,000. In this phenomenon dipolar molecules migrate in an inhomogeneous electric field towards the region of maximum field strength. The field gradient is produced by a 10-μm diameter Pt wire serving as the inner electrode of a cell, and a 2.5-mm diameter cylinder as the outer electrode. An equilibrium exponential concentration gradient is achieved within a few wire radii of the inner electrode in a matter of minutes, making both kinetic and equilibrium measurements feasible. The concentration gradient is monitored by measuring the change in capacitance ΔC of the cell from its value for a uniform solute concentration. The time dependences of ΔC for the build-up of the concentration gradient towards the equilibrium value, and the decay to a uniform concentration after the field is removed have been calculated, using a frictional coefficient and a Boltzmann factor, β1, as the sole adjustable parameters. For low voltages (β1 small), the measured build-up and decay are completely symmetrical, in agreement with theory, and yield the same frictional coefficient. For larger β1, the build-up is faster, reflecting a reduced frictional coefficient due to partial alignment of the long axes of the polymers in the direction of migration. In either case, the decay determines a diffusion constant of randomly aligned molecules, identical to classical diffusion measurement. The value of ΔC at equilibrium, for β1 small, determines μ2F2, where μ is the dipole moment and F is the internal field at the polymer. Combined with a classical dielectric constant measurement, which gives μ2F, both μ and F may be determined, independent of assumptions about cavity shapes. Dielectrophoresis works in alternating as well as constant fields, provided the dipolar orientation can follow the field reversals. The dispersion of dielectrophoresis with frequency is a sensitive measure of the molecular-weight distribution of a given sample. |
