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

• Published in: European journal of organic chemistry Vol. 2018; no. 36; pp. 5054 - 5059
• Main Authors: Ishutkina, Mariia V., Berry, Alice R., Hussain, Rohanah, Khelevina, Olga G., Siligardi, Giuliano, Stulz, Eugen
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 30.09.2018; Wiley Subscription Services, Inc; John Wiley and Sons Inc
• Subjects: Adenosine; Arrays; Assembly; Chemistry; Chemistry, Organic; Chromophores; Communication; Communications; Deoxyribonucleic acid; DNA; Fluorescence; Forensic engineering; Functional organic materials; Gene sequencing; Nucleosides; Optical properties; Organic chemistry; Physical Sciences; Porphyrinoids; Science & Technology; Sizing; Supramolecular chemistry; NONCOVALENT; PORPHYRINS; OLIGONUCLEOTIDE; Fluorescence; HYBRIDIZATION; NILE RED; Supramolecular chemistry; Porphyrinoids; DYE; CONSTRUCTION; ENERGY-TRANSFER; SUPRAMOLECULAR SCAFFOLD; BINDING; Functional organic materials
• DOI: 10.1002/ejoc.201800683
• ISSN: 1434-193X

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. Porphyrin and porphyrazine modified deoxyuridine assemble on oligoadenosine containing single stranded DNA templates in ionic liquids. The high increase in fluorescence of the porphyrazine corresponds to the number of dA binding sites and can thus be used to determine the number of dA containing short tandem repeat units in forensic DNA analysis.