Role of hydrogen bonds in hydrophobicity: the free energy of cavity formation in water models with and without the hydrogen bonds

Madan, Bhupinder; Lee, B.

doi:10.1016/0301-4622(94)00049-2

Cited by 128 publications

(75 citation statements)

References 31 publications

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“…17,18 The dominance of the ΔS cav term in ΔS hyd is also consistent with the previous computational finding that the loss of entropy during the hydration of a solute could be attributed in a large part to the formation of a solvent-excluded volume with only a minor contribution of the electrostatic solute−water interactions. 51,52 Thus, our computational results confirm that the entropic penalty for hydration stems from the repulsive hydrophobic solute−water interactions rather than the electrostatic ones.…”

Section: Resultssupporting

confidence: 85%

Computational Prediction of Molecular Hydration Entropy with Hybrid Scaled Particle Theory and Free-Energy Perturbation Method

Choi

Kang

Park

2015

J. Chem. Theory Comput.

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Despite the importance of the knowledge of molecular hydration entropy (ΔShyd) in chemical and biological processes, the exact calculation of ΔShyd is very difficult, because of the complexity in solute-water interactions. Although free-energy perturbation (FEP) methods have been employed quite widely in the literature, the poor convergent behavior of the van der Waals interaction term in the potential function limited the accuracy and robustness. In this study, we propose a new method for estimating ΔShyd by means of combining the FEP approach and the scaled particle theory (or information theory) to separately calculate the electrostatic solute-water interaction term (ΔSelec) and the hydrophobic contribution approximated by the cavity formation entropy (ΔScav), respectively. Decomposition of ΔShyd into ΔScav and ΔSelec terms is found to be very effective with a substantial accuracy enhancement in ΔShyd estimation, when compared to the conventional full FEP calculations. ΔScav appears to dominate over ΔSelec in magnitude, even in the case of polar solutes, implying that the major contribution to the entropic cost for hydration comes from the formation of a solvent-excluded volume. Our hybrid scaled particle theory and FEP method is thus found to enhance the accuracy of ΔShyd prediction by effectively complementing the conventional full FEP method.

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Section: Resultssupporting

confidence: 85%

Computational Prediction of Molecular Hydration Entropy with Hybrid Scaled Particle Theory and Free-Energy Perturbation Method

Choi

Kang

Park

2015

J. Chem. Theory Comput.

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“…The relatively narrow distribution of cavity sizes in water leads to a decrease in the solubility of all but the very small-sized solute molecules. This point of view should be contrasted with suggestions (14) that the hydrophobic interaction can be understood in terms of the small size of the water molecule alone and that the intrinsic structure of the water molecule is relatively unimportant. The latter approaches basically ignore the hydrogen bonding that…”

Section: Introductionmentioning

confidence: 51%

Hydration for a series of hydrocarbons

Mountain

Thirumalai

1998

Proc. Natl. Acad. Sci. U.S.A.

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The hydrophobic hydration in a series of hydrocarbons is probed by using molecular dynamics simulations. The solutes considered range from methane to octane. Examination of the shapes of the hydration shell suggests that there is no single stable structure surrounding these solutes. The structure of the water molecules around the solute is not significantly perturbed, even for octane, and the hydrogen bond network is essentially preserved. The solutes are accommodated in the voids of the tetrahedral network of water in such a way as to leave the local environment almost intact. The hydrophobic hydration arises primarily because of the plasticity of the hydrogen bond network. Even for octane we find very little evidence for water-mediated interactions between nonbonded carbon atoms, leading us to suggest that the transition to globular conformations can only occur for very long, linear hydrocarbon chains.

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“…Computer simulations [20,21], theoretical analysis [22][23][24][25], and neutron scattering studies [26] are inconsistent with iceberg-like structures. Hence, the restructuring of water around a solvent seems not to play a relevant role in the hydrophobic effect.…”

Section: Hydrophobic Effectmentioning

confidence: 99%

Understanding the role of hydrogen bonds in water dynamics and protein stability

2011

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The mechanisms of cold and pressure denaturation of proteins are a matter of debate, but it is commonly accepted that water plays a fundamental role in the process. It has been proposed that the denaturation process is related to an increase of hydrogen bonds among hydration water molecules. Other theories suggest that the causes of denaturation are the density fluctuations of surface water, or the destabilization of hydrophobic contacts as a consequence of water molecule inclusions inside the protein, especially at high pressures. We review some theories that have been proposed to give insight into this problem, and we describe a coarse-grained model of water that compares well with experiments for proteins' hydration water. We introduce its extension for a homopolymer in contact with the water monolayer and study it by Monte Carlo simulations in an attempt to understand how the interplay of water cooperativity and interfacial hydrogen bonds affects protein stability.

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Role of hydrogen bonds in hydrophobicity: the free energy of cavity formation in water models with and without the hydrogen bonds

Cited by 128 publications

References 31 publications

Computational Prediction of Molecular Hydration Entropy with Hybrid Scaled Particle Theory and Free-Energy Perturbation Method

Computational Prediction of Molecular Hydration Entropy with Hybrid Scaled Particle Theory and Free-Energy Perturbation Method

Hydration for a series of hydrocarbons

Understanding the role of hydrogen bonds in water dynamics and protein stability

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