DNA‐Assisted Self‐Assembly of Pyrene Foldamers

Abstract

The self-organization of oligopyrene foldamers is described. Bi- and tri-segmental oligomers composed of nucleotides and non-nucleosidic, achiral pyrene monomers form double-stranded helical structures, as shown by absorbance, fluorescence, and CD spectroscopy. The mixed nature of alternating aromatic and phosphate groups ensures water solubility which, in turn, favors folding of the aromatic units. Pyrene molecules also assemble though interstrand stacking interactions. Structural organization of the pyrene units is an intrinsic property of the oligoaryl part and takes place independently from the sequence of the attached DNA. Chirality transfer from DNA to the pyrene segment leads to formation of a double helix, in which neighboring pyrene units are, in the present case, twisted in a right-handed manner. Pyrene helicity is most pronounced in a bi-segmental chimera, in which a DNA stem is present only at one end of the pyrene section.

Structural insight into DNA-assembled oligochromophores: crystallographic analysis of pyrene- and phenanthrene-modified DNA in complex with BpuJI endonuclease

“…Their arrangement can be described as a displaced, face-to-face stacking interaction. The proximity of the two pyrenes is in agreement with the observed excimer fluorescence in solutions of DNA hybrids containing 1,8-linked, non-nucleosidic pyrenes in opposite positions (41,61,69). However, the orientation of the two aromatic planes is not parallel, as might be expected, but wedged (25–30°).…”

A new pyrene-based aggregation induced ratiometric emission probe for selective detections of trivalent metal ions and its living cell application

“…Specific colorimetric and ratiometric fluorescence responses toward trivalent metals have been exhibited by pyridinyl-functionalized tetraphenylethene [2]. Moreover, only a few reports of AIE behavior were demonstrated by excimer formations of fluorophores containing pyrene rings [32][33][34][35][36][37][38][39][40][41]. Surprisingly, present results of our pyrene-based fluorophore with Schiff-base probes showed another special aggregation induced ratiometric emission (AIRE) processes upon increasing water content.…”

Influence of perylenediimide–pyrene supramolecular interactions on the stability of DNA-based hybrids: Importance of electrostatic complementarity

“…Recently, we reported that oligoarenotides (oligomers with an alternating phosphodiester-aromatic hydrocarbon motif) exhibit similar structural properties as nucleic acids, and although the aromatic hydrocarbons cannot engage in any sort of Watson–Crick related hydrogen bonding, the individual strands interact via an interstrand stacking motif [45–48]. Herein we describe a series of DNA-based hybrids (Fig.…”