DNA-organized artificial LHCs – testing the limits of chromophore segmentation

Abstract

DNA-organized multi-chromophoric systems containing phenanthrene and pyrene derivatives exhibit a highly efficient excitation energy transfer from phenanthrene to pyrene. The energy transfer also occurs if the phenanthrene antenna is interrupted...

Stabilization of DNA Duplexes and Hairpins by Charge-Transfer Interactions Using DAN:NDI Pairs

“…Modified oligonucleotides are commonly used for applications ranging from therapeutics, − diagnostics, , to supramolecular chemistry and materials. − Among the plethora of modifications that have been described, the replacement of nucleosides by polyaromatic compounds is of particular interest because the resulting π-stacking interactions allow the elaboration of supramolecular architectures having fluorescence or electron transfer properties . Pyrene, − stilbene, , anthraquinone, porphyrin, phenanthrene, , and perylene − are among the most studied aromatic modifications that have been incorporated into DNA structures to increase the thermal stability of the resulting duplexes through π–π interactions. Another possibility to increase the stability of DNA structures is to use charge-transfer (CT) interactions based on the recognition of relatively electron-rich and relatively electron-deficient polyaromatic derivatives like the pyrene:perylenediimide − or dialkoxynaphthalene (DAN):naphthalenetetracarboxylic diimide (NDI) pairs. , The latter is able to self-assemble into alternating face-centered stacking of NDI and DAN moieties to produce foldamers and supramolecular arrangements. ,− …”

Complex DNA Architectonics─Self-Assembly of Amphiphilic Oligonucleotides into Ribbons, Vesicles, and Asterosomes

“…Illustrative examples are natural light-harvesting complexes, in which the spatial organization of the chromophores is crucial for an efficient transfer of excitation energy within large protein complexes. , In nanotechnology, DNA is widely used as a structural element for the bottom-up assembly of nanostructures because the scaffold of the DNA duplex serves as a versatile, robust, and yet highly reliable tool of spatial control. − The specificity and programmability of nucleic acid folding enables the bottom-up creation of multidimensional structures by the DNA origami approach. − Alternatively, DNA nanostructures can be constructed by a self-assembly approach using DNA tiles with sticky ends. − Despite their elegance, both approaches face some limitations, because they often require a set of many, even up to hundreds, different DNA sequences to assemble a desired nanostructure . The integration of unnatural nucleotide surrogates into oligonucleotides introduces additional functionality and extends the scope of application of DNA from the biological context to the field of materials sciences. − Chemically modified DNA conjugates were shown to form supramolecular polymers with potential applications, e.g., in biomedicine for drug delivery systems or in optoelectronic devices. − Recently, we reported the supramolecular assembly of amphiphilic DNA, bearing either phenanthrene or tetraphenylethylene (TPE) hydrophobic ends, into vesicle-shaped objects. , Hydrophobic interactions of DNA sticky ends, as well as spermine-mediated electrostatic interactions, , are among the driving forces that lead to the formation of these DNA-constructed vesicles. Besides serving as sticky ends, hydrophobic TPE overhangs also permit the direct observation of the self-assembly process by fluorescence spectroscopy due to their aggregation-induced emission (AIE) properties. − Potential applications of vesicles consisting of a DNA-constructed membrane comprise, among others, the use as delivery vehicles for biologically active compounds.…”

Heteromeric guanosine (G)-quadruplex derived antenna modules with directional energy transfer

“…[12][13][14][15][16][17][18][19][20][21][22][23][24] Among the various scaffolding technologies, DNA is arguably unrivaled due to the diversity and programmability of 3D structures that can be assembled using DNA, with precision placement of dyes. [25][26][27][28][29][30][31] Further advantages of DNA include its compatibility with biological systems and facile post-synthesis modification.…”