J- vs. H-type assembly: pentamethine cyanine (Cy5) as a near-IR chiroptical reporter.

The DNA-enabled dimerization of pentamethine cyanine (Cy5) dyes was studied by optical methods. The value of cyanine as a chiroptical reporter using a monomer-to-dimer switch is demonstrated. The specific shape of the CD signal and its high intensity are a result of J-type assembly.

Synthesis and properties of squaraine-modified DNA.

The incorporation of squaraines into DNA via the phosphoramidite approach is described. High molar absorptivity, environment-sensitive fluorescence properties and intense CD effects render squaraines valuable building blocks for DNA-based optical probes and nanostructures.

Photon harvesting by excimer-forming multichromophores.

A light-harvesting system based on a DNA-organized oligopyrene-cyanine complex is described. Energy transfer from the pyrene units to the cyanine dye was found to proceed via FRET from locally confined excimers to the acceptor.

Supramolecular polymerization of oligopyrenotides--control by single, natural nucleotides.

Amphiphilic heptapyrenotides (Py(7)) assemble into supramolecular polymers. Here we present a comprehensive spectroscopic study of aggregates and co-aggregates of the non-chiral Py(7) and its mono- or di-substituted nucleotide analogs (Py(7)-N and N-Py(7)-N'). The data show that the formation of supramolecular polymers from oligopyrenotides is highly sensitive to the nature of the attached, chiral auxiliary.

Oligopyrenotides: chiral nanoscale templates for chromophore assembly.

Getting organized: DNA-like supramolecular polymers formed of short oligopyrenotides serve as a helical scaffold for the molecular assembly of ligands. The cationic porphyrin meso-tetrakis(1-methylpyridin-4-yl)porphyrin interacts with the helical polymers in a similar way as with poly(dA:dT).

Signal control by self-assembly of fluorophores in a molecular beacon--a model study.

Pyrene excimer fluorescence is efficiently regulated through formation of π-stacked aggregates between dialkynylpyrene (Y) and perylenediimide (E) residues located in the stem region of a molecular beacon (MB). The building blocks form organized, multichromophoric complexes in the native form. Hybridization to the target results in a conformational reorganization of the chromophores.

Modulation of chiroptical properties by DNA-guided assembly of fluorenes.

The supramolecular organization of fluorene building blocks in a DNA scaffold is described. The molecular assembly into ordered π-aggregates leads to distinct changes in the electronic properties.

Surprising properties of a furo-furanone.

The electronic absorption, fluorescence, and excitation spectra of furo[3,4-c]furanone (1) have been measured in different solvents at different concentrations. We observed a complex dependence of absorption and excitation spectra as a function of the concentration in CH(2)Cl(2) and THF due to aggregate formation. Interestingly, the fluorescence spectra were not affected.

Oligopyrenotides: abiotic, polyanionic oligomers with nucleic acid-like structural properties.

Oligopyrenotides, abiotic oligomers that exhibit significant structural analogies to the nucleic acids, are described. They are composed of achiral, phosphodiester-linked pyrene building blocks and a single chiral 1,2-diaminocyclohexane unit. These oligomers form stable hybrids in aqueous solution.

Nucleic acid-guided assembly of aromatic chromophores.

The rational formation of aromatic chromophore arrays is an intriguing challenge since ordered collectives of chromophores possess properties that are largely different from those of the individual molecules. Therefore, nucleic acids are increasingly used as scaffolds for the construction of multi-chromophore arrays. This tutorial review provides an introduction to the field of nucleic acid-guided chromophore assemblies for non-specialists and a reference point for those familiar with the area by highlighting the recent developments and describing some of the spectroscopic methods used for the study of oligonucleotide-chromophore conjugates.

Photophysical characterization of oligopyrene modules for DNA-based nanosystems.

The photophysics of free pyrenedicarboxamide (Py-DCA) in solution as well as of single-stranded and double-stranded oligonucleotides (ss and ds ONs) containing 1-7 pyrene building blocks per strand were studied by steady-state and time-resolved fluorescence spectroscopy. It was found that the fluorescence quantum yield Phi(F) of free Py-DCA chromophore in solution is rather high (Phi(F) = 0.44).

DNA-assisted self-assembly of pyrene foldamers.

The self-organization of oligopyrene foldamers is described. Bi- and tri-segmental oligomers composed of nucleotides and non-nucleosidic, achiral pyrene monomers form double-stranded helical structures, as shown by absorbance, fluorescence, and CD spectroscopy. The mixed nature of alternating aromatic and phosphate groups ensures water solubility which, in turn, favors folding of the aromatic units.

Dialkynylpyrenes: strongly fluorescent, environment-sensitive DNA building blocks.

Two isomeric dialkynylpyrene phosphoramidites and their incorporation into oligonucleotides are described. The pyrene units closely resemble the well-known perylene bisimide dye PDI with regard to the ability to self-organize within a DNA duplex. In addition, dialkynylpyrenes exhibit significant monomer and remarkably strong excimer fluorescence.

Highly efficient quenching of excimer fluorescence by perylene diimide in DNA.

Pyrene excimer fluorescence is effectively quenched by non-nucleosidic perylene diimides upon DNA duplex formation.

Triazolylpyrenes: synthesis, fluorescence properties, and incorporation into DNA.

Synthesis of 1,6- and 1,8-triazolylpyrenes and their incorporation into oligonucleotides is described. In hybrids, triazolylpyrenes adopt interstrand stacking interactions. Exciton coupling is observed for the duplex containing a pair of the 1,6-isomer indicating a well-defined helical arrangement of the triazolylpyrene building blocks.

DNA containing non-nucleosidic phenanthrene building blocks with asymmetrical linkers.

The synthesis and hybridization properties of oligonucleotides containing phenanthrene building blocks with non-nucleosidic linkers of different length are described. It was found that the length of the linkers, as well as the combination of unequal linkers can have a substantial influence on the thermal stability of the modified DNA.

Self-organization of polyaromatic compounds within DNA.

The structural organization of oligopyrene sections embedded within a DNA framework is described. Absorbance, fluorescence and circular dichroism spectroscopy provide insight into the molecular interactions of the pyrene units.

Spectroscopic properties of pyrene-containing DNA mimics.

DNA mimics containing non-nucleosidic pyrene building blocks are described. The modified oligomers form stable hybrids, although a slight reduction in hybrid stability is observed in comparison to the unmodified DNA duplex. The nature of the interaction between the pyrene residues in single and double stranded oligomers is analyzed spectroscopically.

Characterization of self-assembled monolayers of porphyrins bearing multiple thiol-derivatized rigid-rod tethers.

A series of multithiol-functionalized zinc porphyrins has been prepared and characterized as self-assembled monolayers (SAMs) on Au. The molecules, designated ZnPS(n) (n = 1-4), contain from one to four [(S-acetylthio)methyl]phenylethynylphenyl groups appended to the meso-position of the porphyrin; the other meso-substituents are phenyl groups. For the dithiol-functionalized molecules, both the cis- and the trans-appended structures were examined.

Synthesis of porphyrins bearing hydrocarbon tethers and facile covalent attachment to si(100).

The use of redox-active molecules as the active storage elements in memory chips requires the ability to attach the molecules to an electroactive surface in a reliable and robust manner. To explore the use of porphyrins tethered to silicon via carbosilane linkages, 17 porphyrins have been synthesized. Fourteen porphyrins bear a tether at a single meso site, and three porphyrins bear functional groups at two beta sites for possible two-point attachment.