Abstract
When a dissolved macromolecule is in chemical equilibrium with a free ionic species, the charge configuration, and hence the dipole vector, of the macromolecule is fluctuating. Expressions for the static dielectric constant and the relaxation spectrum of such a mixture are here derived in terms of the components of the mean moment and the root mean square fluctuation moment, the molecular relaxation time constants, and the chemical rate constants of the ionic binding reaction. Contrary to a previous treatment of this problem by Kirkwood and Shumaker (1), it is shown that fluctuations introduce no independent components into the relaxation spectrum.
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Selected References
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- Kirkwood J. G., Shumaker J. B. The Influence of Dipole Moment Fluctuations on the Dielectric Increment of Proteins in Solution. Proc Natl Acad Sci U S A. 1952 Oct;38(10):855–862. doi: 10.1073/pnas.38.10.855. [DOI] [PMC free article] [PubMed] [Google Scholar]