High Shape Persistence in Single Polymer Chains Rigidified with Lateral Hydrogen Bonded Networks

Abstract

Exploiting tapping mode−scanning force microscopy (TM−SFM), we characterized single polymeric chains of poly(isocyanodipeptides) (PICs) equilibrated in quasi two-dimensions on the basal plane of mica surfaces. While the average contour length 〈L〉 of an acid-catalyzed PIC bearing l-alanine-d-alanine methyl ester groups was as high as 5.3 μm, the corresponding Ni-catalyzed product exhibited an 〈L〉 of 70 nm. With a newly devised method based on the statistical analysis of the curvature of polymeric chains on a length scale up to about 100 nm from SFM images, we determined their persistence length 𝓁p. The measured value of 𝓁p = 76 ± 6 nm for both products, independent of the contour length, indicates that the single polymer molecules are very rigid, i.e., even more rigid than the double-stranded DNA. This rigidity is attributed to the helical structure of the polymer backbone and, in particular, to the hydrogen-bonded networks that are present between the alanine moieties in the side chains.