Standard Partial Molal Compressibilities by Ultrasonics. I. Sodium Chloride and Potassium Chloride at 25°

Owen, Benton Brooks; Simons, Harold L.

doi:10.1021/j150550a021

Cited by 96 publications

(56 citation statements)

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“…The relative molar sound velocity increments, [U], determined as described above, were used in conjunction with the partial molar volume, V o , data to calculate the partial molar adiabatic compressibility, K S o , of polynucleotides by using the relationship (27,28):…”

Section: Methodsmentioning

confidence: 99%

A more unified picture for the thermodynamics of nucleic acid duplex melting: A characterization by calorimetric and volumetric techniques

Chalikian

Völker

Plum

et al. 1999

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

235

219

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We use a combination of calorimetric and volumetric techniques to detect and to characterize the thermodynamic changes that accompany helix-to-coil transitions for five polymeric nucleic acid duplexes. Our calorimetric measurements reveal that melting of the duplexes is accompanied by positive changes in heat capacity (⌬C P ) of similar magnitude, with an average ⌬C P value of 64.6 ؎ 21.4 cal deg ؊1 mol ؊1 . When this heat capacity value is used to compare significantly different transition enthalpies (⌬H o ) at a common reference temperature, T ref , we find ⌬H T ref for duplex melting to be far less dependent on duplex type, base composition, or base sequence than previously believed on the basis of the conventional assumption of a near-zero value for ⌬C P . Similarly, our densimetric and acoustic measurements reveal that, at a given temperature, all the ATand AU-containing duplexes studied here melt with nearly the same volume and compressibility changes. In the aggregate, our results, in conjunction with literature data, suggest a more unified picture for the thermodynamics of nucleic acid duplex melting. Specifically, when compared at a common temperature, the apparent large differences present in the literature for the transition enthalpies of different duplexes become much more compressed, and the melting of all-AT-and all-AU-containing duplexes exhibits similar volume and compressibility changes despite differences in sequence and conformation. Thus, insofar as thermodynamic properties are concerned, when comparing duplexes, the temperature under consideration is as important as, if not more important than, the duplex type, the base composition, or the base sequence. This general behavior has significant implications for our basic understanding of the forces that stabilize nucleic acid duplexes. This behavior also is of practical significance in connection with the use of thermodynamic databases for designing probes and for assessing the affinity and specificity associated with hybridization-based protocols used in a wide range of sequencing, diagnostic, and therapeutic applications.Thermodynamic studies of nucleic acids have produced data of both fundamental and practical importance. On the fundamental side, such studies have provided insight into the nature and strength of the forces that stabilize nucleic acids in the myriad of structural states they can assume (1-7). On the practical side, such studies have produced databases that are used to predict the stability and selectivity of hybridization events required in a broad range of nucleic acid-based diagnostic and therapeutic protocols (3, 8-11, 19, 42-44).Three aspects of the current nucleic acid thermodynamic library that are conspicuously deficient are values for the heat capacity change(s), ⌬C P , the volume changes, ⌬V, and the compressibility changes, ⌬K s , which accompany nucleic acid conformational transitions. These deficiencies are of particular concern because ⌬C P , ⌬V, and ⌬K s provide unique insights into the role of solvent i...

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Section: Methodsmentioning

confidence: 99%

A more unified picture for the thermodynamics of nucleic acid duplex melting: A characterization by calorimetric and volumetric techniques

Chalikian

Völker

Plum

et al. 1999

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

235

219

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“…36,37 The resulting values of U were used in conjunction with the V values derived from Eq. (1) to calculate the apparent molar adiabatic compressibility K S using the relationship 38,39 …”

Section: Ultrasonic Velocimetrymentioning

confidence: 99%

The hydration of nucleic acid duplexes as assessed by a combination of volumetric and structural techniques

Chalikian¹,

Völker²,

Srinivasan³

et al. 1999

Biopolymers

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“…The first rigorous treatment is due to Owen and Simons, [5] who derived an equation linking this dependency to the limiting partial molar isothermal compression of salt solutions. Since this equation requires additional thermophysical data, a simpler approach is frequently used in the study of dilute molecular solutions, whereby the speed of ultrasound u depends linearly on the solute concentration c B .…”

Section: Apparent Ultrasound Speed Of a Solutementioning

confidence: 99%

“…Based on the intuitive Natta and Baccaredda [13] model for sound propagation in ideal solutions (see Section 2.2.1), they define an apparent sound velocity of the solute U solute using Equation (5) …”

Section: Apparent Ultrasound Speed Of a Solutementioning

confidence: 99%

Chemical Thermodynamics of Ultrasound Speed in Solutions and Liquid Mixtures

2010

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A comprehensive formalism is developed to treat thermodynamically speed of ultrasound data for solutions and liquid mixtures. For solutions, the apparent speed of ultrasound of a solute is introduced and proposed to take the place of empirically defined quantities. The partial speed of ultrasound of a solute is defined and related to the partial molar volume and partial molar isentropic compression. For liquid mixtures, the concept of speed of sound before mixing pure liquids is presented and used to define the change in speed of ultrasound upon ideal mixing, which is predicted to be generally a negative quantity. A new thermodynamic equation is derived linking the values for excess speed of ultrasound, excess molar volume and excess molar isentropic compression of a mixture, and its applications are discussed. Ideal and excess apparent speeds of ultrasound, as well as ideal and excess partial speeds of ultrasound, are defined for substances making up a liquid mixture. Accurate speeds of ultrasound in 31 mixtures of water with the amphiphile 2-(ethylamino)ethanol at 293.15 K are reported. These data are used to demonstrate the ability of the apparent speed of ultrasound to describe the impact of solutes on sonic properties of solutions and the advantages of analysing thermodynamic properties of binary liquid mixtures in terms of the dependence on composition of Balankina's ratios between excess and ideal values. It is concluded that the new thermodynamic functions defined for speeds of ultrasound in solutions and liquid mixtures give, at the least, equivalent information on molecular aspects to the usual functions related to the isentropic compressibility, without needing density data for this purpose.

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Standard Partial Molal Compressibilities by Ultrasonics. I. Sodium Chloride and Potassium Chloride at 25°

Cited by 96 publications

References 0 publications

A more unified picture for the thermodynamics of nucleic acid duplex melting: A characterization by calorimetric and volumetric techniques

A more unified picture for the thermodynamics of nucleic acid duplex melting: A characterization by calorimetric and volumetric techniques

The hydration of nucleic acid duplexes as assessed by a combination of volumetric and structural techniques

Chemical Thermodynamics of Ultrasound Speed in Solutions and Liquid Mixtures

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