Self‐Assembled Porphyrazine Nucleosides on DNA Templates: Highly Fluorescent Chromophore Arrays and Sizing Forensic Tandem Repeat Sequences

Abstract

The formation of chromophore arrays using a DNA templating approach leads to the creation of supramolecular assemblies, where the optical properties of the overall system can be fine‐tuned to a large extent. In particular, porphyrin derivatives have been shown to be versatile building blocks; mostly covalent chemistry was used for embedding the units into DNA strands. Self‐assembly of porphyrin modified nucleosides, on the other hand, has not been investigated as a simplified approach. We report on the synthesis of a magnesium(II) tetraaza porphine (MgTAP) coupled to deoxyuridine, and array formation on DNA templates which contain well‐defined oligo(dA) segments showing strong fluorescence enhancement which is significantly larger than that with a Zn‐porphyrin. The use of the deep‐eutectic solvent glycholine is essential for successful assembly formation. The system allows for sizing of short tandem repeat markers with multiple adenosines, thus the concept could be adaptable to in vitro forensic DNA profiling with a suitable set of different chromophores on all nucleosides.

Photoswitchable architecture transformation of a DNA-hybrid assembly at the microscopic and macroscopic scale

“…30,31 These assemblies oen exhibit distinct properties compared to the individual molecules, owing to the strong intermolecular interactions. 2,30,31 The hydrogen bond patterns naturally encoded between the DNA base-pairs direct the assembly of supramolecular bers, [32][33][34] hydrogels, [22][23][24]32,35 liquid crystals, 10,36,37 nanoarrays, [38][39][40][41][42][43] and programmed nanoparticles, 44 among others (Fig. 1A).…”

Molecular Chromophore-DNA Architectures With Fullerenes: Optical Properties and Solar Cells

“…In particular, the helical structure as well as the defined distances between the bases and the canonical base pairing precisely control the position of the chromophores and thus suppresses self-quenching that is typically obtained in uncontrolled chromophore aggregates ( Ensslen and Wagenknecht, 2015 ; Vybornyi et al, 2019 ). Modified nucleosides and 2′-deoxynucleosides assemble porphyrins ( Sargsyan et al, 2013 ; Sargsyan et al, 2014 ; Ishutkina et al, 2018 ), naphthalenes ( Janssen et al, 2009a ; Janssen et al, 2009b ; Stevens et al, 2011 ) and pyrenes ( Sezi and Wagenknecht, 2013 ) successfully along single-stranded DNA templates. We realized bichromophore-DNA architectures in a non-covalent and sequence-selective way.…”

Single‐Stranded DNA as Supramolecular Template for One‐Dimensional Palladium(II) Arrays

“…[4][5][6] Nonetheless,s ingle-stranded DNA( ss-DNA) can also participate in the preparation of new nanoscale systems, especially when they are employed to template the assembly of different functional materials in a" bottom-up" approach. [7][8][9][10][11][12][13][14] Moreover,D NA can also be modified to carry specific functionalities. [15] In this context, special attention has been paid to DNAm etallization.…”