Statistical mechanical deconvolution of thermal transitions in macromolecules. II. General treatment of cooperative phenomena

✍ Scribed by Ernesto Freire; Rodney L. Biltonen

• Publisher: Wiley (John Wiley & Sons)
• Year: 1978
• Tongue: English
• Weight: 735 KB
• Volume: 17
• Category: Article
• ISSN: 0006-3525
• DOI: 10.1002/bip.1978.360170213

✦ Synopsis

Abstract

In the preceding article^1^ we demonstrated that the partition function of a system is experimentally accessible from scanning calorimetric data. In this article the general results of the deconvolution theory are applied to the general case of cooperative transitions in macromolecules. It is demonstrated that, in the limit of very large systems, all the relevant molecular averages and molecular distribution functions can be directly obtained from the experiment. In doing this, the method of the grand partition function is used. It is shown that in the case of homopolymers, only one parameter, the stability constant, needs to be explicitly specified for a complete description of the system. Since the partition function is directly evaluated from the experiment, no special assumptions or artificial constraints directed to obtain a mathematically solvable model are required. This result offers the unique opportunity of having direct experimental access to statistical averages of systems in which the partition function cannot analytically be solved. Consequently, the theory can be extended to cooperative transitions occurring in two and three dimensions by introducing cluster distribution functions.