Rigid-rod beta-barrels as lipocalin models: probing confined space by carotenoid encapsulation

Herein, we describe the design, synthesis, structure, and function of synthetic, supramolecular beta-barrel models. Assembly of octi(p-phenylene)s with complementary -Lys-Leu-Lys-NH2 and Glu-Leu-Glu-NH2 side chains yielded water-soluble rigid-rod beta-barrels of precise length and with flexible diameter. A hydrophobic interior was evidenced by guest encapsulation. Host-guest complexes with planarized, monomeric beta-carotene within tetrameric rigid-rod beta-barrels, and disc micellar astaxanthin J-aggregates surrounded by about dodecameric rigid-rod "bicycle tires" were prepared from mixed micelles by dialytic detergent removal. The significance of these findings for future bioorganic chemistry in confined, intratoroidal space is discussed in comparison with pertinent biological examples.