Water molecules mute the dependence of the double-layer potential profile on ionic strength.

We present the results of molecular dynamics simulations of a nanoscale electrochemical cell. The simulations include an aqueous electrolyte solution with varying ionic strength (, concentrations ranging from 0-4 M) between a pair of metallic electrodes held at constant potential difference. We analyze these simulations by computing the electrostatic potential profile of the electric double-layer region and find it to be nearly independent of ionic concentration, in stark contrast to the predictions of standard continuum-based theories.

Bottlebrush polymers with flexible enantiomeric side chains display differential biological properties.

Chirality and molecular conformation are central components of life: biological systems rely on stereospecific interactions between discrete (macro)molecular conformers, and the impacts of stereochemistry and rigidity on the properties of small molecules and biomacromolecules have been intensively studied. Nevertheless, how these features affect the properties of synthetic macromolecules has received comparably little attention. Here we leverage iterative exponential growth and ring-opening metathesis polymerization to produce water-soluble, chiral bottlebrush polymers (CBPs) from two enantiomeric pairs of macromonomers of differing rigidity.

Water-Mediated Interactions Determine Helix Formation of Peptides in Open Nanotubes.

Water-mediated interactions (WMIs) play diverse roles in molecular biology. They are particularly relevant in geometrically confined spaces such as the interior of the chaperonin, at the interface between ligands and their binding partners, and in the ribosome tunnel. Inspired in part by the geometry of the ribosome tunnel, we consider confinement effects on the stability of peptides.

Thermodynamics of Helix-Coil Transitions of Polyalanine in Open Carbon Nanotubes.

Understanding structure formation in polypeptide chains and synthetic polymers encapsulated in pores is important in biology and nanotechnology. We present replica exchange molecular dynamics studies of the phase diagram for α-helix formation of capped polyalanine in nanotubes (NT) open to a water reservoir as a function of the NT diameter and hydrophobicity. A helix forms only in a narrow range of diameters, which surprisingly is comparable to the width of the ribosome tunnel.