Self-Assembly of an Amphiphilic Bile Acid Dimer: A Combined Experimental and Theoretical Study of Its Medium-Responsive Fluorescence

• Published in: Journal of organic chemistry Vol. 87; no. 5; pp. 2255 - 2266
• Main Authors: Santiago-Sampedro, Gerardo I, Aguilar-Granda, Andrés, Torres-Huerta, Aaron, Flores-Álamo, Marcos, Maldonado-Domínguez, Mauricio, Rodríguez-Molina, Braulio, Iglesias-Arteaga, Martín A
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 04.03.2022
• Subjects: Bile Acids and Salts; Models, Molecular; Polymers; Spectrometry, Fluorescence; Water
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.1c01334

This work describes the synthesis and aggregation behavior of a dimeric bile acid derivative in which two steroid cores are bridged by a p-di­(phenylethynyl)­phenylene fluorophore. The studied compound contains three key characteristics: (a) restricted conformational equilibrium in solution, (b) efficient fluorescence conferred by the bridge, and (c) medium responsiveness encoded in the steroid fragments. The incorporation of the three components afforded a compound that generates nano- and micrometric spherical particles with aggregation-responsive fluorescence emission. The observed self-assembly process of the featured molecule was induced by the gradual addition of water to the tetrahydrofuran (THF) solution. This aggregation led to significant changes in fluorescence that went from two bands at λem values of 370 and 390 nm in pure THF to a new spectrum with two maxima at λem values of 395 and 418 nm at high water contents, without a decrease in emission. The observed changes can be ascribed to weakly coupled aggregation, a hypothesis supported by multiscale molecular modeling, which sheds light on the mechanism of the self-assembly of this unconventional amphiphile.