Supramolecular thermodynamics

In thermodynamics, supramolecular thermodynamics is the study of the stabilities, enthalpies and entropies of formation, and free energy changes or evolution spontaneity of systems of supermolecules; also the thermodynamical study of movements of supermolecules or supramolecular structures. [1]

In the study of supramolecular dynamics, one is concerned with not only the classical features, namely geometry, thermodynamics, and kinetics, of interactions, such as in a receptor-substrate supermolecule, but also with internal dynamics or the dynamic cohesion of the atomic and molecular entities of which is composed. [1] As such, in terms of energetics, there exists both "internal thermodynamics" (within the body of the supermolecule) and "interaction thermodynamics" (between supermolecules) of the supermolecules comprising a system.

The term "supramolecular thermodynamics", in a figurative sense, was first used in 1968 by author Mihajlo D. Mesarović. [2] In 1978, Russian physical chemist Georgi Gladyshev began to outline a type of supramolecular thermodynamics in which "supermolecular evolution" of supermolecules or supramolecular systems, in various isothermal-isobaric subsystems of the biosphere, occurs in the direction of a minimum Gibbs free energy of formation. [3]

Difficulties on terminology
At present, the conception of when a molecular entity, such as a host-guest complex, becomes ‘supramolecular’ or what exactly constitutes a supramolecular system, seems to lie in the eye of the beholder. [4] Moreover, in terms of a molecular evolution table view, wherein the evolution and stepwise change of the molecular structure of any dynamic entity can be listed, the use of the term supra-molecular seems to encompass all 3- or 4-element molecular structures and above, including that of the human molecule. In light of this difficulty, some have come to define different classes or species of supermolecules. [5]

1. Lehn, Jean-Marie. (1995). Supramolecular Chemistry, (section 4.5: "Supramolecular Dynamics", pgs. 51-53). New York: VCH.
2. Mesarović, Mihajlo D. (1968). Systems Theory and Biology: Proceedings, (pg. 58). Springer-Verlag.
3. (a) Gladyshev, Georgi, P. (1978). "On the Thermodynamics of Biological Evolution", Journal of Theoretical Biology, Vol. 75, Issue 4, Dec 21, pp. 425-441.
(b) G.P.Gladyshev. (2001). Thermodynamics of biological evolution and aging. Supramolecular thermodynamics is a key to understanding phenomena of life. What is life from a physical chemist's viewpoint
(c) Gladyshev, Georgi, P. “Supramolecular thermodynamics is a key to understanding phenomenon of life. What is life from a physical chemist’s viewpoint”, M., 2002; Second Edition - Moscow – Izevsk, 2003 (In Russian).
(d) Ivanova, V.S., Novikov V. U., and Oksogoev, A.A. (2004). Fractals, Applied Synergetics and Structure Design, (ch. 7: “Thermodynamic Theory Answers the Questions: What is the Driving Force Behind Biological Evolution, and Why do We Age? by Georgi P. Gladyshev, pgs. 103-111). Nova Publishers.
4. Lindoy, L.F. and Atkinson, I.M. (2001). Self-Assembly in Supramolecular Systems (Monographs in Supramolecular Chemistry), (pg. 5). Royal Society of Chemistry.
5. Atwood, J. L. and Steed, Jonathan W. (2004). Encyclopedia of Supramolecular Chemistry. (pg. 1434). CRC Press.

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