Necessity of capillary modes in a minimal model of nanoscale hydrophobic solvation

Vaikuntanathan, Suriyanarayanan; Rotskoff, Grant; Hudson, Alexander; Geissler, Phillip L.

doi:10.1073/pnas.1513659113

Necessity of capillary modes in a minimal model of nanoscale hydrophobic solvation

Journal Article · Tue Mar 08 00:00:00 EST 2016 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1513659113· OSTI ID:1469127

Vaikuntanathan, Suriyanarayanan ^[1]; Rotskoff, Grant ^[2]; Hudson, Alexander ^[3]; Geissler, Phillip L. ^[3]

Univ. of Chicago, IL (United States). Dept. of Chemistry
Univ. of California, Berkeley, CA (United States). Biophysics Graduate Group
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Dept. of Chemistry

Modern theories of the hydrophobic effect highlight its dependence on length scale, emphasizing the importance of interfaces in the vicinity of sizable hydrophobes. We recently showed that a faithful treatment of such nanoscale interfaces requires careful attention to the statistics of capillary waves, with significant quantitative implications for the calculation of solvation thermodynamics. Here, we show that a coarse-grained lattice model like that of Chandler [Chandler D (2005) Nature 437(7059):640-647], when informed by this understanding, can capture a broad range of hydrophobic behaviors with striking accuracy. Specifically, we calculate probability distributions for microscopic density fluctuations that agree very well with results of atomistic simulations, even many SDs from the mean and even for probe volumes in highly heterogeneous environments. This accuracy is achieved without adjustment of free parameters, because the model is fully specified by well-known properties of liquid water. As examples of its utility, we compute the free-energy profile for a solute crossing the air-water interface, as well as the thermodynamic cost of evacuating the space between extended nanoscale surfaces. These calculations suggest that a highly reduced model for aqueous solvation can enable efficient multiscale modeling of spatial organization driven by hydrophobic and interfacial forces.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR) (SC-21). Scientific Discovery through Advanced Computing (SciDAC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1469127

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 16 Vol. 113; ISSN 0027-8424

Publisher:: National Academy of Sciences, Washington, DC (United States)Copyright Statement

Country of Publication:: United States

Language:: English

References (39)

Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
Numerical integration of the cartesian equations of motion of a system with constraints: molecular dynamics of n-alkanes Ryckaert, Jean-Paul; Ciccotti, Giovanni; Berendsen, Herman J. C. Journal of Computational Physics, Vol. 23, Issue 3 https://doi.org/10.1016/0021-9991(77)90098-5	journal	March 1977
Specific Ion Effects at the Air/Water Interface Jungwirth, Pavel; Tobias, Douglas J. Chemical Reviews, Vol. 106, Issue 4 https://doi.org/10.1021/cr0403741	journal	April 2006
The missing term in effective pair potentials Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P. The Journal of Physical Chemistry, Vol. 91, Issue 24 https://doi.org/10.1021/j100308a038	journal	November 1987
Sitting at the Edge: How Biomolecules use Hydrophobicity to Tune Their Interactions and Function Patel, Amish J.; Varilly, Patrick; Jamadagni, Sumanth N. The Journal of Physical Chemistry B, Vol. 116, Issue 8 https://doi.org/10.1021/jp2107523	journal	February 2012
Fluctuations of Water near Extended Hydrophobic and Hydrophilic Surfaces Patel, Amish J.; Varilly, Patrick; Chandler, David The Journal of Physical Chemistry B, Vol. 114, Issue 4 https://doi.org/10.1021/jp909048f	journal	February 2010
Instantaneous Liquid Interfaces Willard, Adam P.; Chandler, David The Journal of Physical Chemistry B, Vol. 114, Issue 5 https://doi.org/10.1021/jp909219k	journal	February 2010
Hydrophobicity at Small and Large Length Scales Lum, Ka; Chandler, David; Weeks, John D. The Journal of Physical Chemistry B, Vol. 103, Issue 22 https://doi.org/10.1021/jp984327m	journal	June 1999
Water conduction through the hydrophobic channel of a carbon nanotube Hummer, G.; Rasaiah, J. C.; Noworyta, J. P. Nature, Vol. 414, Issue 6860 https://doi.org/10.1038/35102535	journal	November 2001
Interfaces and the driving force of hydrophobic assembly Chandler, David Nature, Vol. 437, Issue 7059 https://doi.org/10.1038/nature04162	journal	September 2005
Modulation of hydrophobic interactions by proximally immobilized ions Ma, C. Derek; Wang, Chenxuan; Acevedo-Vélez, Claribel Nature, Vol. 517, Issue 7534 https://doi.org/10.1038/nature14018	journal	January 2015
Adsorption of solutes at liquid–vapor interfaces: insights from lattice gas models Vaikuntanathan, Suriyanarayanan; Shaffer, Patrick R.; Geissler, Phillip L. Faraday Discuss., Vol. 160 https://doi.org/10.1039/C2FD20106B	journal	January 2013
Adsorption of solutes at liquid–vapor interfaces: insights from lattice gas models Vaikuntanathan, Suriyanarayanan; Shaffer, Patrick R.; Geissler, Phillip L. Faraday Discuss., Vol. 160 https://doi.org/10.1039/c2fd20106b	journal	January 2013
Liquid Water: Molecular Correlation Functions from X‐Ray Diffraction Narten, A. H.; Levy, H. A. The Journal of Chemical Physics, Vol. 55, Issue 5 https://doi.org/10.1063/1.1676403	journal	September 1971
An improved coarse-grained model of solvation and the hydrophobic effect Varilly, Patrick; Patel, Amish J.; Chandler, David The Journal of Chemical Physics, Vol. 134, Issue 7 https://doi.org/10.1063/1.3532939	journal	February 2011
A unified formulation of the constant temperature molecular dynamics methods Nosé, Shuichi The Journal of Chemical Physics, Vol. 81, Issue 1 https://doi.org/10.1063/1.447334	journal	July 1984
Particle mesh Ewald: An N ⋅log( N ) method for Ewald sums in large systems Darden, Tom; York, Darrin; Pedersen, Lee The Journal of Chemical Physics, Vol. 98, Issue 12 https://doi.org/10.1063/1.464397	journal	June 1993
Water-like solvation thermodynamics in a spherically symmetric solvent model with two characteristic lengths Buldyrev, S. V.; Kumar, P.; Debenedetti, P. G. Proceedings of the National Academy of Sciences, Vol. 104, Issue 51 https://doi.org/10.1073/pnas.0708427104	journal	December 2007
Static and dynamic correlations in water at hydrophobic interfaces Mittal, J.; Hummer, G. Proceedings of the National Academy of Sciences, Vol. 105, Issue 51 https://doi.org/10.1073/pnas.0809029105	journal	December 2008
Pore opening and closing of a pentameric ligand-gated ion channel Zhu, F.; Hummer, G. Proceedings of the National Academy of Sciences, Vol. 107, Issue 46 https://doi.org/10.1073/pnas.1009313107	journal	November 2010
Extended surfaces modulate hydrophobic interactions of neighboring solutes Patel, A. J.; Varilly, P.; Jamadagni, S. N. Proceedings of the National Academy of Sciences, Vol. 108, Issue 43 https://doi.org/10.1073/pnas.1110703108	journal	October 2011
Elucidating the mechanism of selective ion adsorption to the liquid water surface Otten, D. E.; Shaffer, P. R.; Geissler, P. L. Proceedings of the National Academy of Sciences, Vol. 109, Issue 3 https://doi.org/10.1073/pnas.1116169109	journal	January 2012
Curvature-driven capillary migration and assembly of rod-like particles Cavallaro, M.; Botto, L.; Lewandowski, E. P. Proceedings of the National Academy of Sciences, Vol. 108, Issue 52 https://doi.org/10.1073/pnas.1116344108	journal	December 2011
Solvent fluctuations in hydrophobic cavity–ligand binding kinetics Setny, Piotr; Baron, Riccardo; Michael Kekenes-Huskey, Peter Proceedings of the National Academy of Sciences, Vol. 110, Issue 4 https://doi.org/10.1073/pnas.1221231110	journal	January 2013
Molecular-scale hydrophobic interactions between hard-sphere reference solutes are attractive and endothermic Chaudhari, M. I.; Holleran, S. A.; Ashbaugh, H. S. Proceedings of the National Academy of Sciences, Vol. 110, Issue 51 https://doi.org/10.1073/pnas.1312458110	journal	December 2013
Water-mediated ion-ion interactions are enhanced at the water vapor-liquid interface Venkateshwaran, V.; Vembanur, S.; Garde, S. Proceedings of the National Academy of Sciences, Vol. 111, Issue 24 https://doi.org/10.1073/pnas.1403294111	journal	June 2014
An information theory model of hydrophobic interactions. Hummer, G.; Garde, S.; Garcia, A. E. Proceedings of the National Academy of Sciences, Vol. 93, Issue 17 https://doi.org/10.1073/pnas.93.17.8951	journal	August 1996
Canonical dynamics: Equilibrium phase-space distributions Hoover, William G. Physical Review A, Vol. 31, Issue 3 https://doi.org/10.1103/PhysRevA.31.1695	journal	March 1985
Thermal diffuse x-ray-scattering studies of the water-vapor interface Schwartz, D. K.; Schlossman, M. L.; Kawamoto, E. H. Physical Review A, Vol. 41, Issue 10 https://doi.org/10.1103/PhysRevA.41.5687	journal	May 1990
Gaussian field model of fluids with an application to polymeric fluids Chandler, David Physical Review E, Vol. 48, Issue 4 https://doi.org/10.1103/PhysRevE.48.2898	journal	October 1993
Model of a fluid at small and large length scales and the hydrophobic effect Rein ten Wolde, Pieter; Sun, Sean X.; Chandler, David Physical Review E, Vol. 65, Issue 1 https://doi.org/10.1103/PhysRevE.65.011201	journal	December 2001
Ions at the Air-Water Interface: An End to a Hundred-Year-Old Mystery? Levin, Yan; dos Santos, Alexandre P.; Diehl, Alexandre Physical Review Letters, Vol. 103, Issue 25 https://doi.org/10.1103/PhysRevLett.103.257802	journal	December 2009
Putting Water on a Lattice: The Importance of Long Wavelength Density Fluctuations in Theories of Hydrophobic and Interfacial Phenomena Vaikuntanathan, Suriyanarayanan; Geissler, Phillip L. Physical Review Letters, Vol. 112, Issue 2 https://doi.org/10.1103/PhysRevLett.112.020603	journal	January 2014
Structural Transition in the Ising-Model Interface Weeks, John D.; Gilmer, George H.; Leamy, Harry J. Physical Review Letters, Vol. 31, Issue 8 https://doi.org/10.1103/PhysRevLett.31.549	journal	August 1973
Direct Visual Observation of Thermal Capillary Waves Aarts, D. G. A. L. Science, Vol. 304, Issue 5672 https://doi.org/10.1126/science.1097116	journal	May 2004
M OLECULAR T HEORY OF H YDROPHOBIC E FFECTS : “She is too mean to have her name repeated.” Pratt, Lawrence R. Annual Review of Physical Chemistry, Vol. 53, Issue 1 https://doi.org/10.1146/annurev.physchem.53.090401.093500	journal	October 2002
C ONNECTING L OCAL S TRUCTURE TO I NTERFACE F ORMATION : A Molecular Scale van der Waals Theory of Nonuniform Liquids Weeks, John D. Annual Review of Physical Chemistry, Vol. 53, Issue 1 https://doi.org/10.1146/annurev.physchem.53.100201.133929	journal	October 2002
Dewetting and Hydrophobic Interaction in Physical and Biological Systems Berne, Bruce J.; Weeks, John D.; Zhou, Ruhong Annual Review of Physical Chemistry, Vol. 60, Issue 1 https://doi.org/10.1146/annurev.physchem.58.032806.104445	journal	May 2009
Water in Nonpolar Confinement: From Nanotubes to Proteins and Beyond Rasaiah, Jayendran C.; Garde, Shekhar; Hummer, Gerhard Annual Review of Physical Chemistry, Vol. 59, Issue 1 https://doi.org/10.1146/annurev.physchem.59.032607.093815	journal	May 2008

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Mass Density Fluctuations in Quantum and Classical descriptions of Liquid Water Galib, Mirza; Duignan, Timothy T.; Misteli, Yannick arXiv https://doi.org/10.48550/arxiv.1703.06940	text	January 2017
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