Interpretation of Calorimetric Data from Cooperative Systems

  • Rufus Lumry
Part of the NATO Advance Study Institutes Series book series (ASIC, volume 55)


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.


Free Energy Hydrophobic Effect Total Enthalpy Adiabatic Expansion Compensation Part 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. (1).
    Brandts, J.: 1964, J. Am. Chem. Soc. 86, 4291, 4302.CrossRefGoogle Scholar
  2. (2).
    Benzinger, T.H.: 1969 in Thermodynamics of Life Growth, Held, F., Ed., Adolescent Nutrition and Growth, Appleton Century Croft, New York, Chap. 14; 1971, Nature 229, 100.Google Scholar
  3. (3).
    Frank, H.: 1979, J. Chem. Phys., to be submitted.Google Scholar
  4. (4).
    Lumry, R., Biltonen, R., and Brandts, J.: 1966, Biopolymers 4, 917.CrossRefGoogle Scholar
  5. (5).
    Lumry, R. and Rosenberg, A.: 1976, Colloques Internationaux du C.N.R.S., “Participation energetique de l’eau solvant aux interactions specifiques dans les systems biologiques” 246, 53.Google Scholar
  6. (6).
    Stey, G.: 1967, The Distributions of Single-particle Parameters: Implications for the Structure of Liquid Water, Dissertation, University of Pittsburg.Google Scholar
  7. (7).
    Frank, H. Stey, G.: 1974, Abstracts of the 167th Meeting, American Chemical Soc., Los Angeles, March 31.Google Scholar
  8. (8).
    Stillinger, F. and Ben-Naim, A.: 1969, J. Phys. Chem. 73, 900;CrossRefGoogle Scholar
  9. Ben-Naim, A. and Stillinger, F.: 1972 in Water and Aqueous Solutions: Structure, Thermodynamics and Transport Processes, Horne, R.,Ed., Wiley-Interscience, New York, Chap. 8.Google Scholar
  10. (9).
    Anderson, H.: 1978, submitted to J. Chem. Phys.Google Scholar
  11. (10).
    Tanford, C.: 1973, The Hydrophobic Effect, Wiley-Interscience, New York.Google Scholar
  12. (11).
    Kauzmann, W.: 1959, Adv. Protein Chem. 14.Google Scholar
  13. (12).
    Etzler, F. and Lumry, R.: 1979, to be submitted.Google Scholar
  14. (13).
    Lakowicz, J. and Weber, G.: 1973, Biochemistry 12, 4161.CrossRefGoogle Scholar
  15. (14).
    Lumry, R.: 1974, Proceedings of the First National Symposium on Sickle Cell Disease, DREW publication No. (NIH)75–723, p.165.Google Scholar
  16. (15).
    Lumry, R. and Frank, H: Sept.3–9, 1978, Proc. Sixth Inter-national Biophysics Congress,VII-30-(554).Google Scholar
  17. (16).
    Johnson, F., Eyring, H. and Pollisar, M.: 1954, Kinetic Basis of Molecular Biology, John Wiley, New York.Google Scholar
  18. (17).
    Leo, A., Hansch, C. and Elkins, D.:1971, Chem. Rev. 71, 525.CrossRefGoogle Scholar
  19. (18).
    Benzinger, T.H. and Hammer, C.:1979, to be submitted.Google Scholar
  20. (19).
    Stoesz, J: 1977, Dissertation, University of Minnesota;Google Scholar
  21. Stoesz, J. and Lumry, R.: 1979, to be submitted to Biochemistry.Google Scholar
  22. (20).
    Lumry, R.: September 1978, Proceedings of the Symposium on Polyions, Imai, N., Ed., Kyoto, Japan; 1978, Biophysical J. 000.Google Scholar

Copyright information

© D. Reidel Publishing Company 1980

Authors and Affiliations

  • Rufus Lumry
    • 1
  1. 1.Chemistry DepartmentUniversity of MinnesotaMinneapolisUSA

Personalised recommendations