Diverse Morphologies of Self‐Assemblies from Homoditopic 1,18‐Nucleotide‐Appended Bolaamphiphiles: Effects of Nucleobases and Complementary Oligonucleotides

Abstract The synthesis of 1,18‐nucleotide‐appended bolaamphiphiles (1, 2, 4, and 6) is reported, in which a 3′‐phosphorylated guanidine, adenosine, thymidine, or cytidine is connected to each end of an octadecamethylene chain. Single‐component self‐assemblies and binary self‐assemblies with the complementary oligonucleotides dC₂₀, dT₂₀, dA₂₀, and dG₂₀ are studied by atomic force microscopy, powder X‐ray diffraction analysis, temperature‐dependent UV absorption, circular dichroism, and attenuated total‐reflection Fourier‐transform infrared spectroscopy. The single‐component self‐assembly of 1 forms a two‐dimensional sheet, whereas the binary self‐assembly 1/dC₂₀ gives helical nanofibers. Non‐helical nanofibers are observed for the single‐component self‐assemblies of 2 and 4, and helical nanofibers form from the binary self‐assembly 2/dT₂₀. Interestingly, helical nanorod structures are obtained from the binary self‐assembly 4/dA₂₀, and the aligned nanorods form a nematic phase. The single‐component and binary self‐assemblies from 6 give unilamellar vesicles owing to a lack of stacking interaction between the cytosine moieties.