Control of Energy Transfer Between Pyrene‐ and Perylene‐Nucleosides by the Sequence of DNA‐Templated Supramolecular Assemblies

Abstract

DNA was used as supramolecular scaffold to order chromophores and control their optical properties. Ethynylpyrene as energy donor was attached to 2′‐desoxy‐2‐aminoadenosine that binds selectively to thymidines (T) in the template. Ethynylperylene as acceptor was attached to 2′‐desoxyuridine that is complementary to 2′‐desoxyadenosine (A). This donor‐acceptor pair was assembled along single‐stranded DNA templates of different A−T sequences to investigate the sequence control of the energy transfer between the chromophores. The fluorescence intensities increase in the mixed assemblies along the DNA templates from A10T10 over (AATT)5 to (AT)10, although these templates provide equal numbers of potential binding sites for the two different nucleoside chromophore conjugates and exhibit similar absorbances. This shows that the sequence selective assembly of the two building blocks along DNA templates is programmable and alters the fluorescence readout. Such sequence‐controlled supramolecular chemistry represents the key element for future functional π‐systems in materials for light harvesting of solar energy.

DNA-templated control of chirality and efficient energy transport in supramolecular DNA architectures with aggregation-induced emission

“…Therefore, we followed our established protocol to prepare such DNA-based supramolecular architectures. 32,33 We used 1D and 1L as building blocks and probed their assembly along D-and Lconfigured DNA templates with the sequences A 20 and T 20 by means of optical spectroscopy. Small volumes of the 2'deoxynucleoside stock solutions in DMSO were added to an aqueous solution of the DNA templates (1 mL, 1.25 µM).…”

“…10,11 The non-covalent self-assembly of nucleosides along singlestranded DNA is an important alternative, for instance with naththalenes 12 and porphyrines 13,14 through binding to T 20 or T 40 . We described recently the sequence-selective assembly of pyrenes, [15][16][17] perylenes 18 and nile reds 16,17 as modified 2'-deoxynucleosides along single-stranded DNA templates and mainly ACQ was observed. However, AIE would increase the value of DNA-based materials for optoeletronics.…”

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

“…We realized bichromophore-DNA architectures in a non-covalent and sequence-selective way. Pyrenes and nile reds ( Ensslen et al, 2015 ; Hofsäß et al, 2018 ) or pyrenes and perylenes ( Müller et al, 2020 ) work both as energy transfer pairs. By attaching two dyes to two different nucleosides the optical properties could be programmed by the sequence of the DNA template.…”

Decitabine attenuates dextran sodium sulfate‑induced ulcerative colitis through regulation of immune regulatory cells and intestinal barrier

“…DNA methylation is an epigenetic change that occurs on the cytosine of genomic cpG dinucleotides and plays an important role in the regulation of IBD gene expression (8). Covalent methylation of dNA cpG islands is catalyzed by methyltransferases, which methylate c-5 of cytosine nucleotides (9). The global cytosine methylation pattern in the mammalian genome appears to be established by the complex interaction of at least three independently encoded dNA methyltransferases (dNMT): DNMT1, DNMT3A and DNMT3B (1).…”