Molecular theory and the effects of solute attractive forces on hydrophobic interactions

Chaudhari, Mangesh I.; Rempe, Susan B.; Asthagiri, D.; Tan, L.; Pratt, L. R.

doi:10.1021/acs.jpcb.5b09552

Title: Molecular theory and the effects of solute attractive forces on hydrophobic interactions

Journal Article · Tue Dec 22 00:00:00 EST 2015 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.5b09552· OSTI ID:1237355

Chaudhari, Mangesh I. ^[1]; Rempe, Susan B. ^[1]; Asthagiri, D. ^[2]; Tan, L. ^[3]; Pratt, L. R. ^[3]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Center for Biological and Material Sciences
Rice Univ., Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering
Tulane Univ., New Orleans, LA (United States). Dept. of Chemical and Biomolecular Engineering

The role of solute attractive forces on hydrophobic interactions is studied by coordinated development of theory and simulation results for Ar atoms in water. In this paper, we present a concise derivation of the local molecular field (LMF) theory for the effects of solute attractive forces on hydrophobic interactions, a derivation that clarifies the close relation of LMF theory to the EXP approximation applied to this problem long ago. The simulation results show that change from purely repulsive atomic solute interactions to include realistic attractive interactions diminishes the strength of hydrophobic bonds. For the Ar–Ar rdfs considered pointwise, the numerical results for the effects of solute attractive forces on hydrophobic interactions are opposite in sign and larger in magnitude than predicted by LMF theory. That comparison is discussed from the point of view of quasichemical theory, and it is suggested that the first reason for this difference is the incomplete evaluation within LMF theory of the hydration energy of the Ar pair. With a recent suggestion for the system-size extrapolation of the required correlation function integrals, the Ar–Ar rdfs permit evaluation of osmotic second virial coefficients B₂. Those B₂’s also show that incorporation of attractive interactions leads to more positive (repulsive) values. With attractive interactions in play, B₂ can change from positive to negative values with increasing temperatures. Furthermore, this is consistent with the puzzling suggestions of decades ago that B₂ ≈ 0 for intermediate cases of temperature or solute size. In all cases here, B₂ becomes more attractive with increasing temperature.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program; Consortium for Ocean Leadership (United States)

Contributing Organization:: Tulane Univ., New Orleans, LA (United States); Rice Univ., Houston, TX (United States)

Grant/Contract Number:: AC04-94AL85000; SA 12-05/GoMRI-002

OSTI ID:: 1237355

Alternate ID(s):: OSTI ID: 1347346

Report Number(s):: SAND-2015-20729J; SAND2015-1893J; 555995; TRN: US1600392

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 120, Issue 8; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 23 works

Citation information provided by
Web of Science

References (66)

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
Osmotic Second Virial Coefficient of Methane in Water Koga, K. The Journal of Physical Chemistry B, Vol. 117, Issue 41 https://doi.org/10.1021/jp4085298	journal	October 2013
Thermodynamics of unfolding Kauzmann, Walter Nature, Vol. 325, Issue 6107 https://doi.org/10.1038/325763a0	journal	February 1987
Origin of Entropy Convergence in Hydrophobic Hydration and Protein Folding Garde, Shekhar; Hummer, Gerhard; García, Angel E. Physical Review Letters, Vol. 77, Issue 24 https://doi.org/10.1103/PhysRevLett.77.4966	journal	December 1996
How protein chemists learned about the hydrophobic factor: Protein chemists and the hydrophobic factor Tanford, Charles Protein Science, Vol. 6, Issue 6 https://doi.org/10.1002/pro.5560060627	journal	June 1997
Hydrophobic Solvation NOT via Clathrate Water Cages Silverstein, Todd P. Journal of Chemical Education, Vol. 85, Issue 7 https://doi.org/10.1021/ed085p917.2	journal	July 2008
Molecular Mechanism of Red Cell "Sickling" Murayama, M. Science, Vol. 153, Issue 3732 https://doi.org/10.1126/science.153.3732.145	journal	July 1966
Temperature of polypeptide inverse temperature transition depends on mean residue hydrophobicity Urry, Dan W.; Luan, Chi Hao; Parker, Timothy M. Journal of the American Chemical Society, Vol. 113, Issue 11 https://doi.org/10.1021/ja00011a057	journal	May 1991
[39] Characterization of soluble peptides of elastin by physical techniques Urry, Dan W. Methods in Enzymology https://doi.org/10.1016/0076-6879(82)82096-X	book	January 1982
Secondary Structure Formation and LCST Behavior of Short Elastin-Like Peptides Nuhn, Harald; Klok, Harm-Anton Biomacromolecules, Vol. 9, Issue 10 https://doi.org/10.1021/bm800784y	journal	August 2008
Short elastin-like peptides exhibit the same temperature-induced structural transitions as elastin polymers: implications for protein engineering Reiersen, Herald; Clarke, Anthony R.; Rees, Anthony R. Journal of Molecular Biology, Vol. 283, Issue 1 https://doi.org/10.1006/jmbi.1998.2067	journal	October 1998
Characterization of the Temperature- and Pressure-Induced Inverse and Reentrant Transition of the Minimum Elastin-Like Polypeptide GVG(VPGVG) by DSC, PPC, CD, and FT-IR Spectroscopy Nicolini, C.; Ravindra, R.; Ludolph, B. Biophysical Journal, Vol. 86, Issue 3 https://doi.org/10.1016/S0006-3495(04)74209-5	journal	March 2004
The molecular basis for the inverse temperature transition of elastin11Edited by A. R. Fersht Li, Bin; Alonso, Darwin O. V.; Daggett, Valerie Journal of Molecular Biology, Vol. 305, Issue 3 https://doi.org/10.1006/jmbi.2000.4306	journal	January 2001
Hydrophobic Hydration Is an Important Source of Elasticity in Elastin-Based Biopolymers Li, Bin; Alonso, Darwin O. V.; Bennion, Brian J. Journal of the American Chemical Society, Vol. 123, Issue 48 https://doi.org/10.1021/ja010363e	journal	December 2001
Molecular basis for the extensibility of elastin Li, Bin; Daggett, Valerie Journal of Muscle Research and Cell Motility, Vol. 23, Issue 5/6, p. 561-573 https://doi.org/10.1023/A:1023474909980	journal	October 2002
Temperature-Dependent Conformational Transitions and Hydrogen-Bond Dynamics of the Elastin-Like Octapeptide GVG(VPGVG): A Molecular-Dynamics Study Rousseau, Roger; Schreiner, Eduard; Kohlmeyer, Axel Biophysical Journal, Vol. 86, Issue 3 https://doi.org/10.1016/S0006-3495(04)74210-1	journal	March 2004
Folding and Unfolding of an Elastinlike Oligopeptide: “Inverse Temperature Transition,” Reentrance, and Hydrogen-Bond Dynamics Schreiner, Eduard; Nicolini, Chiara; Ludolph, Björn Physical Review Letters, Vol. 92, Issue 14 https://doi.org/10.1103/PhysRevLett.92.148101	journal	April 2004
Inverse Temperature Transition of a Biomimetic Elastin Model: Reactive Flux Analysis of Folding/Unfolding and Its Coupling to Solvent Dielectric Relaxation ^† Baer, Marcel; Schreiner, Eduard; Kohlmeyer, Axel The Journal of Physical Chemistry B, Vol. 110, Issue 8 https://doi.org/10.1021/jp054805a	journal	March 2006
Temperature-Induced Conformational Transition of a Model Elastin-like Peptide GVG(VPGVG) ₃ in Water Krukau, Aliaksei; Brovchenko, Ivan; Geiger, Alfons Biomacromolecules, Vol. 8, Issue 7 https://doi.org/10.1021/bm070233j	journal	July 2007
Molecular Description of the LCST Behavior of an Elastin-Like Polypeptide Li, Nan K.; Quiroz, Felipe García; Hall, Carol K. Biomacromolecules, Vol. 15, Issue 10 https://doi.org/10.1021/bm500658w	journal	September 2014
Change in Hydration State during the Coil−Globule Transition of Aqueous Solutions of Poly( N -isopropylacrylamide) as Evidenced by FTIR Spectroscopy ^† Maeda, Yasushi; Higuchi, Tomomi; Ikeda, Isao Langmuir, Vol. 16, Issue 19 https://doi.org/10.1021/la0001575	journal	September 2000
Temperature-Induced Phase Transition of Well-Defined Cyclic Poly( N -isopropylacrylamide)s in Aqueous Solution Qiu, Xing-Ping; Tanaka, Fumihiko; Winnik, Françoise M. Macromolecules, Vol. 40, Issue 20 https://doi.org/10.1021/ma071359b	journal	October 2007
Representation of vapor–liquid and liquid–liquid equilibria for binary systems containing polymers: Applicability of an extended flory–huggins equation Bae, Y. C.; Shim, J. J.; Soane, D. S. Journal of Applied Polymer Science, Vol. 47, Issue 7 https://doi.org/10.1002/app.1993.070470707	journal	February 1993
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
Molecular Realism in Default Models for Information Theories of Hydrophobic Effects Gomez, M. A.; Pratt, L. R.; Hummer, G. The Journal of Physical Chemistry B, Vol. 103, Issue 18 https://doi.org/10.1021/jp990337r	journal	May 1999
Contrasting Nonaqueous against Aqueous Solvation on the Basis of Scaled-Particle Theory Ashbaugh, Henry S.; Pratt, Lawrence R. The Journal of Physical Chemistry B, Vol. 111, Issue 31 https://doi.org/10.1021/jp071969d	journal	August 2007
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
Theories of Hydrophobic Effects and the Description of Free Volume in Complex Liquids Pratt, L. R.; Garde, S.; Hummer, G. New Approaches to Problems in Liquid State Theory https://doi.org/10.1007/978-94-011-4564-0_23	book	January 1999
Hydrophobic Effects on a Molecular Scale Hummer, G.; Garde, S.; García, A. E. The Journal of Physical Chemistry B, Vol. 102, Issue 51 https://doi.org/10.1021/jp982873+	journal	November 1998
Hydrophobic Effects and Modeling of Biophysical Aqueous Solution Interfaces Pratt, Lawrence R.; Pohorille, Andrew Chemical Reviews, Vol. 102, Issue 8 https://doi.org/10.1021/cr000692+	journal	July 2002
Scaled-particle theory of dilute aqueous solutions Pierotti, Robert A. The Journal of Physical Chemistry, Vol. 71, Issue 7 https://doi.org/10.1021/j100866a070	journal	June 1967
A scaled particle theory of aqueous and nonaqueous solutions Pierotti, Robert A. Chemical Reviews, Vol. 76, Issue 6 https://doi.org/10.1021/cr60304a002	journal	December 1976
Aqueous Solutions of Nonpolar Gases ¹ Pierotti, Robert A. The Journal of Physical Chemistry, Vol. 69, Issue 1 https://doi.org/10.1021/j100885a043	journal	January 1965
Application of the scaled particle theory to aqueous solutions of nonpolar gases Ben-Naim, Arieh; Friedman, Harold L. The Journal of Physical Chemistry, Vol. 71, Issue 2 https://doi.org/10.1021/j100861a040	journal	January 1967
Theory of the hydrophobic effect Pratt, Lawrence R.; Chandler, David The Journal of Chemical Physics, Vol. 67, Issue 8 https://doi.org/10.1063/1.435308	journal	October 1977
Benzene-benzene interaction in aqueous solution Rossky, Peter J.; Friedman, Harold L. The Journal of Physical Chemistry, Vol. 84, Issue 6 https://doi.org/10.1021/j100443a005	journal	March 1980
Theory of Hydrophobic Effects Pratt, L. R. Annual Review of Physical Chemistry, Vol. 36, Issue 1 https://doi.org/10.1146/annurev.pc.36.100185.002245	journal	October 1985
A prototype hydrophobic interaction. The dimerization of benzene in water Tucker, Edwin E.; Christian, Sherril D. The Journal of Physical Chemistry, Vol. 83, Issue 3 https://doi.org/10.1021/j100466a026	journal	February 1979
Vapor pressure studies of hydrophobic association. Thermodynamics of fluorobenzene in dilute aqueous solution Bernal, Pedro; Christian, Sherril D.; Tucker, Edwin E. Journal of Solution Chemistry, Vol. 15, Issue 11 https://doi.org/10.1007/BF00646033	journal	November 1986
Effects of solute–solvent attractive forces on hydrophobic correlations Pratt, Lawrence R.; Chandler, David The Journal of Chemical Physics, Vol. 73, Issue 7 https://doi.org/10.1063/1.440541	journal	October 1980
Molecular dynamics study of the hydrophobic interaction in an aqueous solution of krypton Watanabe, Kyoko; Andersen, Hans C. The Journal of Physical Chemistry, Vol. 90, Issue 5 https://doi.org/10.1021/j100277a019	journal	February 1986
Entropy of association of methane in water: a new molecular dynamics computer simulation Smith, David E.; Zhang, Ling; Haymet, A. D. J. Journal of the American Chemical Society, Vol. 114, Issue 14 https://doi.org/10.1021/ja00040a068	journal	July 1992
Free energy, entropy, and internal energy of hydrophobic interactions: Computer simulations Smith, David E.; Haymet, A. D. J. The Journal of Chemical Physics, Vol. 98, Issue 8 https://doi.org/10.1063/1.464809	journal	April 1993
Role of attractive methane-water interactions in the potential of mean force between methane molecules in water Asthagiri, D.; Merchant, Safir; Pratt, Lawrence R. The Journal of Chemical Physics, Vol. 128, Issue 24 https://doi.org/10.1063/1.2944252	journal	June 2008
Local molecular field theory for the treatment of electrostatics Rodgers, Jocelyn M.; Weeks, John D. Journal of Physics: Condensed Matter, Vol. 20, Issue 49 https://doi.org/10.1088/0953-8984/20/49/494206	journal	November 2008
Cavity Expulsion and Weak Dewetting of Hydrophobic Solutes in Water Hummer, Gerhard; Garde, Shekhar Physical Review Letters, Vol. 80, Issue 19 https://doi.org/10.1103/PhysRevLett.80.4193	journal	May 1998
The Potential Distribution Theorem and Models of Molecular Solutions Beck, Tom L.; Paulaitis, Michael E.; Pratt, Lawrence R. Cambridge University Press https://doi.org/10.1017/CBO9780511536663	book	January 2006
Intermolecular Forces and the Nature of the Liquid State: Liquids reflect in their bulk properties the attractions and repulsions of their constituent molecules Widom, B. Science, Vol. 157, Issue 3787 https://doi.org/10.1126/science.157.3787.375	journal	July 1967
Mean-Field Approximation to the Hydrophobic Hydration in the Liquid–Vapor Interface of Water Abe, Kiharu; Sumi, Tomonari; Koga, Kenichiro The Journal of Physical Chemistry B, Vol. 120, Issue 8 https://doi.org/10.1021/acs.jpcb.5b10169	journal	November 2015
Accurate thermodynamics for short-ranged truncations of Coulomb interactions in site-site molecular models Rodgers, Jocelyn M.; Weeks, John D. The Journal of Chemical Physics, Vol. 131, Issue 24 https://doi.org/10.1063/1.3276729	journal	December 2009
On the efficient and accurate short-ranged simulations of uniform polar molecular liquids Rodgers, Jocelyn M.; Hu, Zhonghan; Weeks, John D. Molecular Physics, Vol. 109, Issue 7-10 https://doi.org/10.1080/00268976.2011.554332	journal	March 2011
Relationship between local molecular field theory and density functional theory for non-uniform liquids Archer, A. J.; Evans, R. The Journal of Chemical Physics, Vol. 138, Issue 1 https://doi.org/10.1063/1.4771976	journal	January 2013
Non-van der Waals Treatment of the Hydrophobic Solubilities of CF ₄ Asthagiri, D.; Ashbaugh, H. S.; Piryatinski, A. Journal of the American Chemical Society, Vol. 129, Issue 33 https://doi.org/10.1021/ja071037n	journal	August 2007
Equilibrium Structure of Simple Liquids Chandler, David; Weeks, John D. Physical Review Letters, Vol. 25, Issue 3 https://doi.org/10.1103/PhysRevLett.25.149	journal	July 1970
Studies of the Thermodynamic Properties of Hydrogen Gas in Bulk Water Sabo, Dubravko; Varma, Sameer; Martin, Marcus G. The Journal of Physical Chemistry B, Vol. 112, Issue 3 https://doi.org/10.1021/jp075459v	journal	January 2008
GROMACS 4: Algorithms for Highly Efficient, Load-Balanced, and Scalable Molecular Simulation Hess, Berk; Kutzner, Carsten; van der Spoel, David Journal of Chemical Theory and Computation, Vol. 4, Issue 3 https://doi.org/10.1021/ct700301q	journal	February 2008
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
Settle: An analytical version of the SHAKE and RATTLE algorithm for rigid water models Miyamoto, Shuichi; Kollman, Peter A. Journal of Computational Chemistry, Vol. 13, Issue 8 https://doi.org/10.1002/jcc.540130805	journal	October 1992
Hydration of Kr(aq) in Dilute and Concentrated Solutions Chaudhari, Mangesh I.; Sabo, Dubravko; Pratt, Lawrence R. The Journal of Physical Chemistry B, Vol. 119, Issue 29 https://doi.org/10.1021/jp508866h	journal	September 2014
PACKMOL: A package for building initial configurations for molecular dynamics simulations Martínez, L.; Andrade, R.; Birgin, E. G. Journal of Computational Chemistry, Vol. 30, Issue 13 https://doi.org/10.1002/jcc.21224	journal	October 2009
THE weighted histogram analysis method for free-energy calculations on biomolecules. I. The method Kumar, Shankar; Rosenberg, John M.; Bouzida, Djamal Journal of Computational Chemistry, Vol. 13, Issue 8 https://doi.org/10.1002/jcc.540130812	journal	October 1992
Kirkwood–Buff Integrals for Finite Volumes Krüger, Peter; Schnell, Sondre K.; Bedeaux, Dick The Journal of Physical Chemistry Letters, Vol. 4, Issue 2 https://doi.org/10.1021/jz301992u	journal	December 2012
How to apply the Kirkwood–Buff theory to individual species in salt solutions Schnell, Sondre K.; Englebienne, Pablo; Simon, Jean-Marc Chemical Physics Letters, Vol. 582 https://doi.org/10.1016/j.cplett.2013.07.043	journal	September 2013
Temperature and Pressure Dependence of Methane Correlations and Osmotic Second Virial Coefficients in Water Ashbaugh, Henry S.; Weiss, Katie; Williams, Steven M. The Journal of Physical Chemistry B, Vol. 119, Issue 20 https://doi.org/10.1021/acs.jpcb.5b02056	journal	May 2015
A Monte Carlo simulation of the hydrophobic interaction Pangali, C.; Rao, M.; Berne, B. J. The Journal of Chemical Physics, Vol. 71, Issue 7 https://doi.org/10.1063/1.438701	journal	January 1979
Deblurred Observation of the Molecular Structure of an Oil−Water Interface Ashbaugh, Henry S.; Pratt, Lawrence R.; Paulaitis, Michael E. Journal of the American Chemical Society, Vol. 127, Issue 9 https://doi.org/10.1021/ja042600u	journal	March 2005

Cited By (7)

Water hydrogen degrees of freedom and the hydrophobic effect Islam, Naeyma; Flint, Mahalia; Rick, Steven W. The Journal of Chemical Physics, Vol. 150, Issue 1 https://doi.org/10.1063/1.5053239	journal	January 2019
Evaluation of second osmotic virial coefficients from molecular simulation following scaled-particle theory Barnett, J. Wesley; Ashbaugh, Henry S. Molecular Simulation, Vol. 45, Issue 17 https://doi.org/10.1080/08927022.2019.1639698	journal	July 2019
Utility of chemical computations in predicting solution free energies of metal ions Chaudhari, Mangesh I.; Pratt, Lawrence R.; Rempe, Susan B. Molecular Simulation, Vol. 44, Issue 2 https://doi.org/10.1080/08927022.2017.1342127	journal	June 2017
On the behavior of the osmotic second virial coefficients of gases in aqueous solutions: Rigorous results, accurate approximations, and experimental evidence Chialvo, Ariel A.; Crisalle, Oscar D. The Journal of Chemical Physics, Vol. 150, Issue 12 https://doi.org/10.1063/1.5047525	journal	March 2019
Methane Hydration‐Shell Structure and Fragility Wu, Xiangen; Lu, Wanjun; Streacker, Louis M. Angewandte Chemie, Vol. 130, Issue 46 https://doi.org/10.1002/ange.201809372	journal	October 2018
The water molecule arrangement over the side chain of some aliphatic amino acids: A quantum chemical and bottom‐up investigation Lanza, Giuseppe; Chiacchio, Maria A. International Journal of Quantum Chemistry, Vol. 120, Issue 9 https://doi.org/10.1002/qua.26161	journal	January 2020
Methane Hydration‐Shell Structure and Fragility Wu, Xiangen; Lu, Wanjun; Streacker, Louis M. Angewandte Chemie International Edition, Vol. 57, Issue 46 https://doi.org/10.1002/anie.201809372	journal	November 2018

Similar Records

Role of Solute Attractive Forces in the Atomic-Scale Theory of Hydrophobic Effects

Journal Article · Wed May 16 00:00:00 EDT 2018 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry · OSTI ID:1237355

Gao, Ang; Tan, Liang; Chaudhari, Mangesh I.; +4 more

Effects of solute--solvent attractive forces on hydrophobic correlations

Journal Article · Wed Oct 01 00:00:00 EDT 1980 · J. Chem. Phys.; (United States) · OSTI ID:1237355

Pratt, L R; Chandler, D

Hydrophobic interactions and osmotic second virial coefficients for methanol in water

Journal Article · Tue Jan 01 00:00:00 EST 1980 · J. Solution Chem.; (United States) · OSTI ID:1237355

Pratt, L R; Chandler, D

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS

Title: Molecular theory and the effects of solute attractive forces on hydrophobic interactions

Citation Formats

References (66)

Cited By (7)

Similar Records

Related Subjects