Scaled-particle theory of dilute aqueous solutions

Pierotti, Robert A.

doi:10.1021/j100866a070

Cited by 70 publications

(50 citation statements)

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“…In this work the Lennard-Jones pair potential parameters presented are those obtained when the first option is adopted to allow comparisons with other solvents, the parameters of which were obtained in the same way. from the solubility data of rare gases at different temperatures (23), and l1 = -1.48 X lop4 K-' from enthalpy solution data (24). The agreement between both methods is ordinary (4,7,24).…”

Section: Resultsmentioning

confidence: 99%

Solubility of nonpolar gases in 2,6-dimethylcyclohexanone

Gallardo¹,

López²,

Urieta³

et al. 1990

Can. J. Chem.

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URIETA, and CELSO GUTIERREZ LOSA. Can. J. Chem. 68, 435 (1990).Solubility measurements of He, Ne, Ar, Kr, Xe, Hz, DZ, N2, CH4, C2H4, C2H6, CF4, SF6, and C 0 2 in 2,6-dimethylcyclohexanone at temperatures 273.15 to 303.15 K and at a gas partial pressure of 101.33 kPa are reported. Standard changes in Gibbs energy, enthalpy, and entropy for the dissolution process at 298.15 K are also presented. Results for both solubility and thermodynamic functions are compared with those for cyclohexanone and 2-methylcyclohexanone. The scaled particle theory is used to obtain the effective Lennard-Jones (6,12) pair potential parameters for 2,6-dimethylcyclohexanone and, from these, the values it predicts for the solubility of the studied gases in the solvent are obtained.

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Section: Resultsmentioning

confidence: 99%

Solubility of nonpolar gases in 2,6-dimethylcyclohexanone

Gallardo¹,

López²,

Urieta³

et al. 1990

Can. J. Chem.

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“…The cavitation term was determined using Pierotti's scaled particle theory (Pierotti, 1976), while the van der Waals' term was evaluated [Eqn (4)] by means of the relation with the molecular surface area :…”

Section: Gas Phase Conformations Conformational Preferences Ofmentioning

confidence: 99%

Intrinsic Conformational Preferences of the Hoechst Dye Family and their Influence on DNA Binding

Vega

Coll

Alemán

1996

European Journal of Biochemistry

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Quantum mechanical calculations have been used to investigate the molecular conformation of the Hoechst family of DNA-binding dyestuffs. Compounds in which the phenolic substituent adopts either a meta or (tam position were studied. Two different environments have been considered, which are the gas phase and aqueous solution; the conformation in aquaeous solution has been modeled through a selfconsistent reaction field strategy. The results clearly indicate that Hoechst dyes do not adopt a planar conformation and that the degree of planarity is controlled by the external environment. A comparison with experimental data reveals that the conformation of Hoechst dyes in the gas phase is similar to that observed in DNA complexes by X-ray crystallography. In aqueous solution, the conformation deviates from planarity more than in the gas phase, since non-bonded interactions with the solvent offset the loss of conjugative interactions. The role of the drug conformation in the binding mechanism with DNA is discussed.

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“…The resulting small-solute hydration thermodynamics has been predicted successfully by approaches that take into account the molecular-scale density fluctuations in bulk water, including scaled-particle theory (5,19) (see ref. 20 for a recent review), , the Gaussian field model (21), an information theory model (22), and Lum-Chandler-Weeks (LCW) theory (23).…”

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Static and dynamic correlations in water at hydrophobic interfaces

Mittal

Hummer

2008

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

137

144

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We study the static and dynamic properties of the water-density fluctuations in the interface of large nonpolar solutes. With the help of extensive molecular dynamics simulations of TIP4P water near smooth spherical solutes, we show that for large solutes, the interfacial density profile is broadened by capillary waves. For purely repulsive solutes, the squared width of the interface increases linearly with the logarithm of the solute size, as predicted by capillary-wave theory. The apparent interfacial tension extracted from the slope agrees with that of a free liquid-vapor interface. The characteristic length of local density fluctuations is Ϸ0.5 nm, measured along the arc, again consistent with that of a free liquid-vapor interface. Probed locally, the interfacial density fluctuations exhibit large variances that exceed those expected for an ideal gas. Qualitatively consistent with theories of the free liquid-vapor interface, we find that the water interface near large and strongly nonpolar solutes is flickering, broadened by capillarywave fluctuations. These fluctuations result in transitions between locally wet and dry regions that are slow on a molecular time scale.capillary waves ͉ drying transition ͉ hydrophobic effect ͉ surface tension T he hydration structure and thermodynamics of simple nonpolar solutes in water is central to a molecular understanding of many biological self-assembly processes, including protein folding and the formation of lipid membranes (1-4). To understand the water-induced conformational changes in biopolymers that lead to functional structures, it is critical to study not only the effects of water on these molecules but also the reverse, i.e., the modified behavior of water in the vicinity of these molecules. To avoid the inherent chemical and structural complexities of present in biological molecules, it is instructive to consider model systems with tunable degrees of freedom. Arguably the simplest such model system is a smooth spherical particle immersed in a water bath (5-18). Such a rudimentary solute model captures two key factors in solvation, the size of the solute and the strength of its interactions with water.Small, methane-sized solutes are accommodated by water with only minor disruptions of the bulk hydrogen-bond network. The resulting small-solute hydration thermodynamics has been predicted successfully by approaches that take into account the molecular-scale density fluctuations in bulk water, including scaled-particle theory (5, 19) (see ref. 20 for a recent review), Pratt-Chandler theory (8), the Gaussian field model (21), an information theory model (22), and Lum-Chandler-Weeks (LCW) theory (23). With the addition of a large repulsive solute, it becomes impossible for water molecules to maintain their bulk hydrogen-bond structure (24), which also affects the wetting behavior. At ambient conditions the contact theorem predicts a near-zero water density at a flat hard wall (5). Based on this rigorous limit and an interpolation formula, Stillinger anticipated that...

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Scaled-particle theory of dilute aqueous solutions

Cited by 70 publications

References 1 publication

Solubility of nonpolar gases in 2,6-dimethylcyclohexanone

Solubility of nonpolar gases in 2,6-dimethylcyclohexanone

Intrinsic Conformational Preferences of the Hoechst Dye Family and their Influence on DNA Binding

Static and dynamic correlations in water at hydrophobic interfaces

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