Distance distributions of end-labeled curved bispeptide oligomers by electron spin resonance.

We demonstrate the synthesis of a series of spin-labeled curved oligomers to determine their end-to-end lengths and distance distributions using electron spin resonance. We synthesize shape-persistent macromolecules from conformationally restricted, asymmetric monomers that are coupled through pairs of amide bonds to create water-soluble, spiro-ladder oligomers with well-defined three-dimensional structures. We synthesized seven different macromolecules, each containing eight monomers but differing in the sequence to create macromolecules with different curved shapes. The ends of the oligomers were labeled with nitroxide spin probes, and double electron−electron resonance (DEER) electron spin resonance (ESR) experiments were carried out to obtain quantitative information about the shapes and flexibility of the oligomers. The most probable end-to-end distance of the oligomers ranges from 23 to 36 A, a range of length that we previously accessed by assembling rod-like homo-oligomers that contain 4−8 bisamin...