Compression Isotherms of Monomolecular Films of 7β-alkyl Cholic Acid Derivatives on an Acidic Aqueous Substrate and Their Interactions with Lecithin Reveal the Conformations of the Alkyl Chain and Steroid Skeleton

7β-烷基胆酸衍生物单分子膜在酸性水溶液基底上的压缩等温线及其与卵磷脂的相互作用揭示了烷基链和甾体骨架的构象

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Abstract

This study analyzed the compression isotherms of 7β-alkyl cholic acid derivatives and compared them to those of cholic and deoxycholic acids to elucidate their orientation and molecular interactions (acidic aqueous substrate-pH 2; NaCl concentration-3 M; temperature-T = 298.15 K). It was found that the compression isotherm of the 7β-octyl derivative of cholic acid in the monomolecular layer is most similar to the compression isotherm of deoxycholic acid. In 7β-alkyl derivatives of cholic acid, the hydrophobic interaction energy in their aggregates from a monomolecular film increased with the length of the alkyl chain. However, this energy did not increase linearly with C atoms, suggesting the existence of a conformational equilibrium. In binary mixtures of the tested bile acids and lecithin, only the 7β-octyl derivatives of cholic acid and deoxycholic acid had orientations in which the steroid skeleton had a "vertical" position, i.e., only the C3 OH group was immersed in the aqueous substrate, which resulted in the maximum hydrophobic interaction with lecithin. In 7β-octyl derivatives, part of the octyl chain probably also participated in the interaction with lecithin. In 7β-propyl and 7β-butyl derivatives, C7 alkyl groups sterically shielded the C7 α-axial OH group. However, in the 7β-ethyl derivative the C7 OH group was not additionally sterically shielded, so this derivative, similarly to cholic acid, partially dissolved in the aqueous substrate after the collapse point.

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