Structure‐Sensitive and Self‐Assembled Helical Pyrene Array Based on DNA Architecture

Mayer-Enthart, Elke; Wagenknecht, Hans‐Achim

doi:10.1002/anie.200504210

Cited by 133 publications

(68 citation statements)

References 42 publications

(40 reference statements)

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“…These aromatic compounds interact favorably through stacking interactions. In work by Wagenknecht, clusters of aromatic chromophores covalently attached to uridine were also shown to form a helical π-array along the major groove of the DNA duplex (15, 16). Strongly enhanced emission from clusters of stacked pyrene-labeled uridines was observed.…”

Section: Introductionmentioning

confidence: 99%

Polyfluorophore Excimers and Exciplexes as FRET Donors in DNA

Teo

Kool

2009

Bioconjugate Chem.

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We describe studies aimed at testing whether oligomeric exciplex-and excimer fluorophores conjugated to DNA have the potential to act as donors for energy transfer by the Förster mechanism. Oligodeoxyfluorosides (ODFs) are composed of stacked, electronically interacting fluorophores replacing the bases on a DNA scaffold. The monomer chromophores in the twenty tetramer-length ODFs studied here include pyrene (Y), benzopyrene (B), perylene (E), dimethylaminostilbene (D), and a nonfluorescent spacer (S); these are conjugated in varied combinations at the 3' end of a 14mer DNA probe sequence. In the absence of an acceptor chromophore, many of the ODF-DNAs show broad, unstructured long-wavelength emission peaks characteristic of excimer and exciplex excited states, similar to what has been observed for unconjugated ODFs. Although such delocalized excited states have been widely studied, we know of no prior report of their use in FRET. We tested the ability of the twenty ODFs to donate energy to Cy5 and TAMRA dyes conjugated to a complementary strand of DNA, with these acceptors oriented either at the near or far end of the ODF-conjugated probes. Results showed that a number of the ODF fluorophores exhibited relatively efficient energy transfer characteristic of the Förster mechanism, as judged by drops in donor emission quantum yield and fluorescence lifetime, accompanied by increases in intensity of acceptor emission bands. Excimer/exciplex bands in the donors were selectively quenched while shorter-wavelength monomer emission stayed relatively constant, consistent with the notion that the delocalized excited states, rather than individual fluorophores, are the donors. Interestingly, only specific sequences of ODFs were able to act as donors, while others did not, even though their emission wavelengths were similar. The new FRET donors possess large Stokes shifts, which can be beneficial for multiple applications. In addition, all ODFs can be excited at a single wavelength; thus, ODFs may be candidates as "universal FRET donors", thus allowing multicolor FRET of multiple species to be carried out with one excitation.

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Section: Introductionmentioning

confidence: 99%

Polyfluorophore Excimers and Exciplexes as FRET Donors in DNA

Teo

Kool

2009

Bioconjugate Chem.

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“…grooves, interior base stacking region, or end-of-helix modification; b) examples of modified nucleosides and base surrogates used to make functional DNA. [8] Fig. 3. a) First examples of porphyrinic modifications at the 5'-end of DNA; b) short linkers for efficient chiral transfer onto porphyrin which is used as chiroptical marker; c) a porphyrin embedded within the base stacking region of DNA.…”

Section: First-generation Porphyrin-dna Systemsmentioning

confidence: 99%

Porphyrin-modified DNA as Construction Material in Supramolecular Chemistry and Nano-architectonics

Stulz¹

2015

Chimia

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An overview is given on the developments of using porphyrin-modified DNA for the construction of functional assemblies. Strategies for the synthesis and characterisation are presented alongside selected applications where the porphyrin modification has proven to be particularly useful, but also revealed its limitations. We also discuss implications on property and behaviour of the porphyrin-DNA, where similar issues could arise using other hydrophobic and bulky substituents on DNA.

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“…The helical array of chromophores, such as a pyrene group along the polymer backbone, is of particular interest because such a system may produce a possible molecular wire through which excitation energy and charge may be one-dimensionally transported. To this end, the pyrene group has often been introduced at the side chains of helical RNA, 30 DNA, 31,32 peptides, 33,34 and artificial polymers, [35][36][37][38] and their changes in the fluorescence spectra due to a helical array of the pyrenes have been investigated. However, a pyrene-bound helical polymer, which shows an inversion of the helicity, has not been reported.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and chiroptical properties of a helical poly(phenylacetylene) bearing optically active pyrene pendants

2007

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A novel poly(phenylacetylene) derivative bearing optically active pyrene moieties as the pendant groups (poly-(R)-1) was prepared by the polymerization of the corresponding monomer (R)-1 in the presence of a rhodium catalyst, and its chiroptical property was investigated. Poly-(R)-1 exhibited an induced circular dichroism (ICD) in the polymer backbone region due to the predominantly one-handed helical conformation. The ICD pattern dramatically changed and was accompanied by inversion of the Cotton effect sign in response to a change in the temperature and solvent, indicating that poly-(R)-1 underwent a helix-helix transition in response to the external stimuli.

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Structure‐Sensitive and Self‐Assembled Helical Pyrene Array Based on DNA Architecture

Abstract: Five times is more than fivefold: The helical π‐stacked array of pyrene‐modified uridine shows a strong fluorescence enhancement that is structure sensitive to base mismatches. As the fluorescence is highly sequence dependent, it can serve as a structure‐sensitive probe for DNA.

Cited by 133 publications

References 42 publications

Polyfluorophore Excimers and Exciplexes as FRET Donors in DNA

Polyfluorophore Excimers and Exciplexes as FRET Donors in DNA

Porphyrin-modified DNA as Construction Material in Supramolecular Chemistry and Nano-architectonics

Synthesis and chiroptical properties of a helical poly(phenylacetylene) bearing optically active pyrene pendants

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