Cooperative and Noncooperative Assembly of Oligopyrenotides Resolved by Atomic Force Microscopy

Rudnev, Alexander; Malinovskii, Vladimir L.; Nussbaumer, Alina Laura; Mishchenko, Artem; Häner, Robert; Wandlowski, Thomas (2012). Cooperative and Noncooperative Assembly of Oligopyrenotides Resolved by Atomic Force Microscopy. Macromolecules, 45(15), pp. 5986-5992. Washington, D.C.: American Chemical Society 10.1021/ma3007619

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The supramolecular assembly of amphiphilic oligopyrenotide
building blocks (covalently linked heptapyrene, Py7) is studied
by atomic force microscopy (AFM) in combination with optical
spectroscopy. The assembly process is triggered in a controlled
manner by increasing the ionic strength of the aqueous oligomer
solution. Cooperative noncovalent interactions between individual
oligomeric units lead to the formation of DNA-like supramolecular
polymers. We also show that the terminal attachment of a single
cytidine nucleotide to the heptapyrenotide (Py7-C) changes the association process from a cooperative (nucleation−elongation)
to a noncooperative (isodesmic) regime, suggesting a structure misfit between the cytidine and the pyrene units. We also
demonstrate that AFM enables the identification and characterization of minute concentrations of the supramolecular products,
which was not accessible by conventional optical spectroscopy.

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