Comment on “Global thermodynamics of hydrophobic cavitation, dewetting, and hydration” [J. Chem. Phys. <b>123</b>, 184504 (2005)]

Graziano, Giuseppe

doi:10.1063/1.2213607

Cited by 4 publications

(2 citation statements)

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“…Thus, although many models faithfully reveal the free energy change of the association of two hydrophobic entities, a lot fewer successes have been marked up in regard to accurately determining the enthalpy or entropy changes (first derivatives of the initial experiment). Additionally, success in modeling heat capacity changes (a second derivative of the experiment) has been limited to spherical representations of methane [53][54][55][56].…”

Section: The Hydrophobic Effectmentioning

confidence: 99%

Van Der Waals Interactions and the Hydrophobic Effect

Gibb

2011

Chemosensors

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Section: The Hydrophobic Effectmentioning

confidence: 99%

Van Der Waals Interactions and the Hydrophobic Effect

Gibb

2011

Chemosensors

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“…toronto.edu study. [63][64][65][66][67] Notably, this intriguing phenomenon 68,69 provided rationalization for several otherwise puzzling behaviors of compact unfolded states of proteins, 70 even though such a positive heat capacity change was not predicted by bulk-phase solvent accessible surface area considerations. 49 Indeed, recent atomic ͑explicit-water͒ simulations have shown that nonadditivity is significant for hydrophobic interactions among more than two nonpolar solutes.…”

Section: Introductionmentioning

confidence: 99%

Pressure and temperature dependence of hydrophobic hydration: Volumetric, compressibility, and thermodynamic signatures

Moghaddam

Chan

2007

The Journal of Chemical Physics

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The combined effect of pressure and temperature on hydrophobic hydration of a nonpolar methanelike solute is investigated by extensive simulations in the TIP4P model of water. Using test-particle insertion techniques, free energies of hydration under a range of pressures from 1 to 3000 atm are computed at eight temperatures ranging from 278.15 to 368.15 K. Corresponding enthalpy, entropy, and heat capacity accompanying the hydration process are estimated from the temperature dependence of the free energies. Partial molar and excess volumes calculated using pressure derivatives of the simulated free energies are consistent with those determined by direct volume simulations; but direct volume determination offers more reliable estimates for compressibility. At 298.15 K, partial molar and excess isothermal compressibilities of methane are negative at 1 atm. Partial molar and excess adiabatic (isentropic) compressibilities are estimated to be also negative under the same conditions. But partial molar and excess isothermal compressibilities are positive at high pressures, with a crossover from negative to positive compressibility at approximately 100-1000 atm. This trend is consistent with experiments on aliphatic amino acids and pressure-unfolded states of proteins. For the range of pressures simulated, hydration heat capacity exhibits little pressure dependence, also in apparent agreement with experiment. When pressure is raised at constant room temperature, hydration free energy increases while its entropic component remains essentially constant. Thus, the increasing unfavorability of hydration under raised pressure is seen as largely an enthalpic effect. Ramifications of the findings of the authors for biopolymer conformational transitions are discussed.

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