The Ionization Behavior of Fatty Acids and Bile Acids in Micelles and Membranes

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Abstract
The ionization behavior of carboxylic acids including aliphatic chain fatty acids and bile acids in solutions, micelles, membranes and proteins is of considerable biological interest. The 13C nuclear magnetic resonance chemical shift of carboxyl carbon of a variety of acids has been shown to be a linear function of the state of ionization of the carboxyl group. Thus, by measuring the chemical shift as a function of the amount of acid or base added to a solution, the state of ionization and the apparent pKa of the carboxyl group may be determined. The method is illustrated in this paper using butyric acid, and results (given as apparent pKa values) are tabulated for a variety of fatty acids and cholic acid in different environments such as monomeric solutions, micelles, membranes and bound to albumin. The apparent pKa varies greatly depending upon the environment. For instance, the apparent pKa of oleic acid is about 4.2 when bound to albumin whereas it is about 7.5 when incorporated in the bilayer of a phospholipid vesicle. Cholic acid shows similar changes in the apparent pKa, being approximately 5.2 in sodium taurocholate micelles and at least 6.8 in phospholipid vesicles. The use of 13C nuclear magnetic resonance (NMR) and, in particular, I3C NMR of 13C-enriched carboxyl groups provides a method for direct observation of the state of ionization of the carboxyl group in biologically interesting acids. Such techniques may be adapted for use in biological systems, such as cells or tissues.