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A set of bolaamphiphiles containing L-glutamic acid head-groups and different hybrid linkers (BECA) were found hierarchically co-assembled with nucleobase (such as thymine, cytosine, adenine, or guanine) to form different supramolecular nanostructures in aqueous solution.For adenine, the co-assembly with bolaamphiphiles containing different spacer lengths would produce nanoparticles with diverse diameter and surface roughness.While in the case of guanine, no co-assemblies from different bolaamphiphiles can be obtained due to the bad solubility.