Diffusion of Rodlike Polymers: Pulsed Gradient Spin Echo NMR of Poly(γ-stearyl-α,l-glutamate) Solutions and the Importance of Helix Stability.

Abstract

Many natural and synthetic polymers and particles have a rodlike shape, leading to important and intriguing solution behavior, such as high intrinsic viscosities and liquid crystalline phases. Much of what is known about suspensions of rods has been learned by studying helical polypeptides, even though such molecules are not perfectly rigid, smooth cylinders. Previous optical tracer self-diffusion studies of poly(γ-benzyl-α,l-glutamate) (PBLG) revealed that the molecule initially resists topological constraints imposed by neighboring molecules, but diffusion strongly decreases as concentration rises beyond a certain number density. In contrast, the tracer self-diffusion coefficient of truly rigid tobacco mosaic virus begins decreasing immediately with concentration. We used pulsed gradient spin echo NMR to measure another polypeptide, poly(γ-stearyl-α,l-glutamate) (PSLG), to gain physical insight into the question of polypeptide diffusion in crowded isotropic solutions. The PSLG molecule, with long alkyl sidechains, is semiflexible like PBLG but does not exhibit the same ability to evade topological constraints. Instead, PSLG follows a simple exponential decay, D/ DKR = A e(-κν/ν*) + B, where DKR is the Kirkwood-Riseman expectation for rod diffusion, ν is the number density of rods, ν* is the Onsager expectation for the number density at the onset of liquid crystal formation, A = 1 ± 0.1, B = 0.1 ± 0.01, and κ = 4.5 ± 0.5. The results emphasize the importance of helix stability when choosing rodlike polypeptides as model systems, particularly with regard to the chain ends.