4-4-difluoro-4-bora-3a-4a-diaza-s-indacene and pyrene

There is an increasing need for fluorescent nucleic acid probes that are able to sense genetic variations without the application of enzymes. The incorporation of organic fluorophores either as DNA base modifications or as DNA base substitutions represents a powerful and versatile method for such new fluorescent DNA assays. Multiple labeling of oligonucleotides using several adjacent chromophore-modified DNA bases yields fluorescence enhancement and modulation that are sensitive to single-base mismatches in the complementary oligonucleotide. Charge transfer processes that cause fluorescence quenching are DNA-base mediated and occur over several base pairs distance. Our "DETEQ" setup, consisting of a fluorescence DNA base substitution and the charge acceptor as a second modification two base pairs away, allows the homogeneous detection of single-base mutations simply by fluorescence readout. This could lead to new DNA microarrays which are based on charge transfer processes and can be analyzed by commonly used fluorescence readout techniques.

Topics: Base Composition; Base Pairing; Benzopyrenes; Boron Compounds; Buffers; DNA; Fluorescent Dyes; Models, Chemical; Mutation; Nucleotides; Oligonucleotide Array Sequence Analysis; Phenothiazines; Pyrenes; RNA; Spectrometry, Fluorescence

We envisioned a new approach for achieving triplet-triplet annihilation-assisted photon upconversion based on the rational design of a heavy-atom-free, all-organic and photoactivatable triplet-triplet synergistic multichromophoric molecular assembly. This single molecular architecture is easily built by covalently anchoring triplet-annihilator units (pyrenes) to a triplet-photosensitizer moiety (BODIPY), to improve the effectiveness and probability of the required triplet-triplet energy transfer and the ulterior triplet-triplet annihilation. This unprecedented design takes advantage of the high synthetic accessibility and chemical versatility of the

Topics: Energy Transfer; Photons; Pyrenes

The facile synthesis and in vitro activity of a library of heavy atom-free BODIPY-anthracene, -pyrene dyads (BAD-13-BPyrD-19) and a control (BODIPY 20) are reported. We demonstrate that singlet oxygen produced from dyad triplet states formed from charge-separated states is sufficient to induce cytotoxicity in human breast cancer cells (MDA-MB-468) at micromolar concentrations. The compounds in this series are promising candidates for photodynamic therapy, especially BAD-17 which displays significant photocytotoxicity (15% cell viability) at a concentration of 5 × 10-7 M, with minimal toxicity (89% cell viability) in the absence of light.

Topics: Anthracenes; Boron Compounds; Cell Line; Cell Survival; Photochemotherapy; Photosensitizing Agents; Pyrenes; Singlet Oxygen

Topics: Animals; Boron Compounds; Fluorescent Dyes; Indoles; Isoindoles; Melanoma; Mice; Molecular Structure; Pyrenes; Tumor Cells, Cultured

A new series of dendronized bodipys containing pyrene units was synthesized and characterized. Their optical and photophysical properties were determined by absorption and fluorescence spectroscopy. This series includes three different compounds. The first one has an anisole group linked to the bodipy unit, which was used as the reference compound. In the second, the bodipy core is linked to a zero generation dendron with one pyrene unit. The third compound contains a first generation Fréchet-type dendron bearing two pyrene units. In this work, the combination pyrene-bodipy was selected as the donor-acceptor pair for this fluorescence resonance energy transfer (FRET) study. Doubtless, these two chromophores exhibit high quantum yields, high extinction coefficients, and both their excitation and emission wavelengths are located in the visible region. This report presents a FRET study of a novel series of pyrene-bodipy dendritic molecules bearing flexible spacers. We demonstrated via spectroscopic studies that FRET phenomena occur in these dyads.

Topics: Anthracenes; Boron Compounds; Fluorescence Resonance Energy Transfer; Pyrenes; Spectrum Analysis

An extended molecular array, comprising three distinct types of chromophores and two additional redox-active subunits, that harvests photons over most of the visible spectral range has been synthesized and characterised. The array exhibits a rich variety of electrochemical waves when examined by cyclic voltammetry but assignment can be made on the basis of control compounds and molecular orbital calculations. Stepwise electronic energy transfer occurs along the molecular axis, corresponding to a gradient of excitation energies, to populate the lowest-energy excited state of the ultimate acceptor. The latter species, which absorbs and emits in the far-red region, enters into light-induced charge transfer with a terminal amine group. The array is relatively stable under illumination with white light but degrades slowly via a series of well-defined steps, the first of which is autocatalytic. One of the main attributes of this system is the capability to harvest an unusually high fraction of sunlight while providing protection against exposure to UV light.

Topics: Biomimetics; Boron Compounds; Coloring Agents; Electrochemical Techniques; Energy Transfer; Light; Models, Molecular; Oxidation-Reduction; Photosynthesis; Pyrenes; Spectrometry, Fluorescence

The chromophores pyrene and bordipyrromethenylbenzene directly linked to the 5-position of uridine are tolerated and recognized as thymine derivatives by DNA polymerases in primer extension experiments.

Topics: Base Sequence; Boron Compounds; Catalysis; DNA-Directed DNA Polymerase; Molecular Sequence Data; Molecular Structure; Oligonucleotides; Pyrenes; Spectrometry, Fluorescence; Uridine

Molecules bearing a 4,4-difluoro-8-(aryl)-1,3,5,7-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene (bodipy) core and 1-pyrenyl-1-phenyl-4-(1-ethynylpyrene), or 1-phenyl-4-[1-ethynyl-(6-ethynylpyrene)pyrene] units were constructed in a step-by-step procedure based on palladium(0)-promoted cross-coupling reactions with the required preconstructed modules. X-ray structures of single crystals reveal a twisted arrangement of the two chromophores. In one case, an almost perfect orthogonal arrangement is found. These dyes are strongly luminescent in solution and display rich electrochemistry in which all redox processes of the bodipy and pyrene fragments are clearly resolved. The absorption spectra indicate that the bodipy and pyrene chromophores are spectrally isolated, thereby inducing a large "virtual" Stokes shift. The latter is realised by efficient transfer of intramolecular excitation energy by the Förster dipole-dipole mechanism. The rate of energy transfer depends on the structure of the dual-dye system and decreases as the centre-to-centre separation increases. The energy transfer efficiency, however, exceeds 90 % in all cases. The linkage of two pyrene residues by an ethyne group leads to a decrease in the energy-transfer efficiency, with the two polycycles acting as a single chromophore. The directly linked bodipy-pyrene dual dye binds to DNA and operates as an efficient solar concentrator when dispersed in plastic.

Topics: Boron Compounds; Energy Transfer; Fluorescent Dyes; Pyrenes; X-Ray Diffraction

Surfactant protein B (SP-B) enhances lipid insertion into the alveolar air/liquid interface upon inhalation. The aim of this study was (i) to apply a palette of tests for a detailed biochemical and biophysical characterization of SP-B and (ii) to use these tests to compare native SP-B with a fluorescent (Bodipy) SP-B analog. The method of labeling was fast and resulted in a covalent fluorophore-protein bond. The ability of both proteins to spread a surfactant film on top of a buffer surface was determined in a spreading tray using the Wilhelmy plate technique to allow detection of alterations in surface tension and calculation of spreading velocities. In a captive bubble surfactometer surface tensions of spread films were measured. Similar biophysical properties were found for both native and Bodipy-labeled SP-B. It is concluded that the combination of tests used allows detection of small differences in structure and activity between the two proteins.

Topics: 1,2-Dipalmitoylphosphatidylcholine; Animals; Boron Compounds; Bronchoalveolar Lavage; Buffers; Cattle; Chromatography, High Pressure Liquid; Circular Dichroism; Fluorescent Dyes; Glass; Micelles; Phosphatidylcholines; Phosphatidylglycerols; Proteolipids; Pulmonary Surfactants; Pyrenes; Sequence Analysis, Protein; Spectrometry, Mass, Electrospray Ionization; Structure-Activity Relationship; Surface Tension