Thermophoresis of a Colloidal Rod: Contributions of Charge and Grafted Polymers

In this study, we investigated the thermodiffusion behavior of a colloidal model system as a function of the Debye length, λ_DH, which is controlled by the ionic strength. Our system consists of an fd-virus grafted with poly(ethylene glycol) (PEG) with a molecular mass of 5000 g mol^-1. The results are compared with recent measurements on a bare fd-virus and with results of PEG. The diffusion coefficients of both viruses are comparable and increase with the increasing Debye length. The thermal diffusion coefficient, D_T, of the bare virus increases strongly with the Debye length, whereas D_T of the grafted fd-virus shows only a very weak increase. The Debye length dependence of both systems can be described with an expression derived for charged rods using the surface charge density and an offset of D_T as adjustable parameters. It turns out that the ratio of the determined surface charges is inverse to the ratio of the surfaces of the two systems, which means that the total charge remains almost constant. The determined offset of the grafted fd-virus describing the chemical contributions is the sum of D_T of PEG and the offset of the bare fd-virus. At high λ_DH, corresponding to the low ionic strength, the S_T values of both colloidal model systems approach each other. This implies a contribution from the polymer layer, which is strong at short λ_DH and fades out for the longer Debye lengths, when the electric double layer reaches further than the polymer chains and therefore dominates interactions with the surrounding water.