title: Supramolecular polymerization of oligopyrenotides--control by single, natural nucleotides.
abstract: Amphiphilic heptapyrenotides (Py(7)) assemble into supramolecular polymers. Here we present a comprehensive spectroscopic study of aggregates and co-aggregates of the non-chiral Py(7) and its mono- or di-substituted nucleotide analogs (Py(7)-N and N-Py(7)-N'). The data show that the formation of supramolecular polymers from oligopyrenotides is highly sensitive to the nature of the attached, chiral auxiliary. A single natural nucleotide may be sufficient for the fine tuning of the aggregates' properties by changing the mechanism of aggregation from an isodesmic to a nucleation-elongation process, which results in a high degree of amplification of chirality in the formed supramolecular polymers. Watson-Crick complementarity does not play a significant role, since co-aggregates of oligomers modified with complementary nucleotides show no signs of supramolecular polymerization. Depending on the nucleotide, the helical sense of the polymers is shifted to an M-helix or a P-helix. The findings demonstrate the value of oligopyrenotides as oligomeric building blocks for the generation of optically active supramolecular polymers.
authors.affiliation: Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland.
authors.forename: Alina L
authors.initials: AL
authors.lastname: Nussbaumer
authors.forename: Florent
authors.initials: F
authors.lastname: Samain
authors.forename: Vladimir L
authors.initials: VL
authors.lastname: Malinovskii
authors.forename: Robert
authors.initials: R
authors.lastname: Häner
mesh_terms: D000241:Adenosine / Q000737:chemistry; D001688:Biological Products / Q000737:chemistry; D003562:Cytidine / Q000737:chemistry; D015394:Molecular Structure; D009711:Nucleotides / Q000737:chemistry*; D058105:Polymerization; D011721:Pyrenes / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D001688:Biological Products; D009711:Nucleotides; D011721:Pyrenes; D003562:Cytidine; C030984:pyrene; D000241:Adenosine