Sitting at the edge: How biomolecules use hydrophobicity to tune their interactions and function

Abstract

Water near hydrophobic surfaces is like that at a liquid-vapor interface, where fluctuations in water density are substantially enhanced compared to that in bulk water. Here we use molecular simulations with specialized sampling techniques to show that water density fluctuations are similarly enhanced, even near hydrophobic surfaces of complex biomolecules, situating them at the edge of a dewetting transition. Consequently, water near these surfaces is sensitive to subtle changes in surface conformation, topology, and chemistry, any of which can tip the balance towards or away from the wet state, and thus significantly alter biomolecular interactions and function. Our work also resolves the long-standing puzzle of why some biological surfaces dewet and other seemingly similar surfaces do not.

12 pages, 4 figures

References in corpus (4)

• Canonical sampling through velocity-rescaling
• The influence of geometry, surface character and flexibility on the permeation of ions and water through biological pores
• Extended surfaces modulate and can catalyze hydrophobic effects
• Quantifying density fluctuations in volumes of all shapes and sizes using indirect umbrella sampling

Cited by in corpus (18)

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• Understanding Hydrophobic Effects: Insights from Water Density Fluctuations
• Critical fluctuations in proteins native states
• Drying and Wetting Transitions of a Lennard-Jones Fluid: Simulations and Density Functional Theory
• Rough interfaces, accurate predictions: The necessity of capillary modes in a minimal model of nanoscale hydrophobic solvation
• Density depletion and enhanced fluctuations in water near hydrophobic solutes: identifying the underlying physics
• Wetting and cavitation pathways on nanodecorated surfaces
• Hydrophobicity Scaling of Aqueous Interfaces by an Electrostatic Mapping
• Water Density Fluctuations Relevant to Hydrophobic Hydration are Unaltered by Attractions
• Understanding the physics of hydrophobic solvation
• Mechanosensitive Channel Activation by Diffusio-Osmotic Force
• A classical density functional theory for solvation across length scales
• Simulations of HIV capsid protein dimerization reveal the effect of chemistry and topography on the mechanism of hydrophobic protein association
• Measures of Fluctuations for a Liquid Near Critical Drying
• Intra-chain organisation of hydrophobic residues controls inter-chain aggregation rates of amphiphilic polymers
• Hydration Free Energies of Linear Alkanes: Systematic Deviations in Common Water Models and Their Correction