Abstract
Recent developments initiated by a suggestion of Benzinger show that enthalpy and entropy quantities each contain two parts, one which contributes to the free energy and one which does not but which reflects enthalpy and entropy fluctuations behavior. In water and most biological systems, the fluctuations parts may dominate the work-doing (motive) parts in which case free energy is not simply related to total enthalpy and entropy. There is increasing evidence the enthalpy fluctuations have been exploited by nature in the evolution of many biological functions and the abnormal behavior of cold water is entirely due to such fluctuations. As an example, the hydrophobic effect is reanalyzed to show that the poor solubility of hydrophobic molecules in water is due to unfavorable enthalpy and not to unfavorable entropy. The classical formulations of the thermodynamics are still correct for free energy calculations but serious discrepancies can arise in attempts to formulate test hypotheses of mechanism using enthalpy, entropy and volume or pressure information. Biological membranes and proteins are similar but more complicated than water solutions. A brief consideration of some consequences of this similarity is given as a basis for subsequent discussion of the interaction of small molecules with proteins.
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Lumry, R. (1980). Interpretation of Calorimetric Data from Cooperative Systems. In: Braibanti, A. (eds) Bioenergetics and Thermodynamics: Model Systems. NATO Advance Study Institutes Series, vol 55. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-9035-7_29
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DOI: https://doi.org/10.1007/978-94-009-9035-7_29
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