Flexible, charged biopolymers in monovalent and mixed-valence salt: Regimes of anomalous electrostatic stiffening and of salt insensitivity.

TitleFlexible, charged biopolymers in monovalent and mixed-valence salt: Regimes of anomalous electrostatic stiffening and of salt insensitivity.
Publication TypeJournal Article
Year of Publication2021
AuthorsInnes-Gold, Sarah N., David R. Jacobson, Philip A. Pincus, Mark J. Stevens, and Omar A. Saleh
JournalPhys Rev E
Date Published2021 Jul

The conformations of biological polyelectrolytes (PEs), such as polysaccharides, proteins, and nucleic acids, affect how they behave and interact with other biomolecules. Relative to neutral polymers, PEs in solution are more locally rigid due to intrachain electrostatic repulsion, the magnitude of which depends on the concentration of added salt. This is typically quantified using the Odijk-Skolnick-Fixman (OSF) electrostatic-stiffening model, in which salt-dependent Debye-Hückel (DH) screening modulates intrachain repulsion. However, the applicability of this approach to flexible PEs has long been questioned. To investigate this, we use high-precision single-molecule elasticity measurements to infer the scaling with salt of the local stiffness of three flexible biopolymers (hyaluronic acid, single-stranded RNA, and single-stranded DNA) in both monovalent and mixed-valence salt solutions. In monovalent salt, we collapse the data across all three polymers by accounting for charge spacing, and find a common power-law scaling of the electrostatic persistence length with ionic strength with an exponent of 0.66±0.02. This result rules out simple OSF pictures of electrostatic stiffening. It is roughly compatible with a modified OSF picture developed by Netz and Orland; alternatively, we posit the exponent can be explained if the relevant electrostatic screening length is the interion spacing rather than the DH length. In mixed salt solutions, we find a regime where adding monovalent salt, in the presence of multivalent salt, does not affect PE stiffness. Using coarse-grained simulations, and a three-state model of condensed, chain-proximate, and bulk ions, we attribute this regime to a "jacket" of ions surrounding the PE that regulates the chain's effective charge density as ionic strength varies. The size of this jacket in simulations is again consistent with a screening length controlled by interion spacing rather than the DH length. Taken together, our results describe a unified picture of the electrostatic stiffness of polyelectrolytes in the mixed-valence salt conditions of direct relevance to cellular and intercellular biological systems.

Alternate JournalPhys Rev E
PubMed ID34412211