Structure and Dynamics of Self-Assembling β-Sheet Peptide Tapes by Dynamic Light Scattering

Abstract

Oligomeric peptides can be designed which undergo one-dimensional self-assembly in solution to form β-sheet tapes a single molecule in thickness and micrometers in length. ¹ In this paper, we present the first systematic investigation of the size, shape, dynamics, and interactions of β-sheet tapes formed by a self-assembling 24-residue peptide, K24, in 2-chloroethanol, over a wide range of peptide concentrations c (c: 10^-7−1 mM), using photon correlation spectroscopy. The tapes behave like semiflexible chains with persistence lengths of several hundred nanometers and much longer contour lengths, even at c ≈ 0.1 nM. The polarized q-dependent light-scattering intensity I fits a model of a prolate object with major and minor axes α ≈ 630 nm and β ≈ 40 nm. This is an unexpected result in view of the previous theoretical predictions that tapelike polymers could form oblate coinlike structures in solution. ² This experimentally observed behavior is attributed to the pronounced twist and bend of the β-tapes, which do not allow them to form the coinlike structures, but instead they favor the formation of elongated polymers. At c* ≈ 10^-2 mM, the tapes are seen to start overlapping and forming networks with unusually large mesh sizes (e.g., ca. 400 nm at 15 μM), much larger than those of conventional polymers. With increasing peptide concentration the mesh size decreases and the network becomes a physical gel at c ≈ 0.4 mM. These semidilute solutions are characterized by one main relaxation mode associated with the cooperative diffusion of the entangled tape network, and a weaker slower mode, associated with gel cluster formation. The concentration dependence of ξ (ξ(c) ∼ c^-0.34) is much weaker compared to the expected scaling for Gaussian or swollen chains (ξ(c) ∼ c^-1 for Gaussian chains, or ξ(c) ∼ c^-3/4 for swollen ones), but is not inconsistent with the expected scaling for rigid rods. On the basis of the concentration dependencies of the light-scattering intensity I and of the cooperative diffusion coefficient D, the cooperative friction coefficient f_c is found to display a stronger concentration dependence (f_c ∼ c^1.34) than in the case of semidilute flexible and semiflexible polymer solutions (f_c ∼c^0.5). ³ Thus, we may conclude that the network of entangled tapes approximates in its behavior that of semirigid polymers.