1714-27-8Relevant articles and documents
Recognition of double-stranded DNA using energetically activated duplexes with interstrand zippers of 1-, 2- or 4-pyrenyl-functionalized O2′-alkylated RNA monomers
Karmakar, Saswata,Madsen, Andreas S.,Guenther, Dale C.,Gibbons, Bradley C.,Hrdlicka, Patrick J.
, p. 7758 - 7773 (2014)
Despite advances with triplex-forming oligonucleotides, peptide nucleic acids, polyamides and-more recently-engineered proteins, there remains an urgent need for synthetic ligands that enable specific recognition of double-stranded (ds) DNA to accelerate studies aiming at detecting, regulating and modifying genes. Invaders, i.e., energetically activated DNA duplexes with interstrand zipper arrangements of intercalator-functionalized nucleotides, are emerging as an attractive approach toward this goal. Here, we characterize and compare Invaders based on 1-, 2- and 4-pyrenyl-functionalized O2′-alkylated uridine monomers X-Z by means of thermal denaturation experiments, optical spectroscopy, force-field simulations and recognition experiments using DNA hairpins as model targets. We demonstrate that Invaders with +1 interstrand zippers of X or Y monomers efficiently recognize mixed-sequence DNA hairpins with single nucleotide fidelity. Intercalator-mediated unwinding and activation of the double-stranded probe, coupled with extraordinary stabilization of probe-target duplexes (ΔTm/modification up to +14.0 °C), provides the driving force for dsDNA recognition. In contrast, Z-modified Invaders show much lower dsDNA recognition efficiency. Thus, even very conservative changes in the chemical makeup of the intercalator-functionalized nucleotides used to activate Invader duplexes, affects dsDNA-recognition efficiency of the probes, which highlights the importance of systematic structure-property studies. The insight from this study will guide future design of Invaders for applications in molecular biology and nucleic acid diagnostics.
Synthesis method of OLED intermediate 2-bromopyrene
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Paragraph 0050-0063, (2019/02/13)
The invention provides a synthesis method of OLED intermediate 2-bromopyrene. The method comprises the steps of firstly using 1-amino-2-bromopyrene as a raw material, using diazotization deamination method to obtain a 2-bromopyrene crude product; putting the 2-bromopyrene crude product ethyl acetate with a usage amount being 1.5 to 2.5 times by weight of the crude product, conducting heating to reflux, and then lowering the temperature to 20+/-2 DEG C to achieve crystallization, so as to achieve refining of the 2-bromopyrene crude product and finally obtain a 2-bromopyrene pure product with apurity of 99.5% or more. According to the invention, 1-amino-2-bromopyrene is used to prepare 2-bromopyrene, the yield is high, and the finally obtained 2-bromopyrene is high in purity. Meanwhile, theinvention provides a method of using 2-aminopyrene to react with a brominating reagent for prepare 1-amino-2-bromopyrene with a high yield, and the price of 1-aminopyrene is low. Compared with the prior art, the synthesis method disclosed by the invention can reduce the cost of preparing 2-bromopyrene.
Synthesis of 2-and 2,7-functionalized pyrene derivatives: An application of selective C-H borylation
Crawford, Andrew G.,Liu, Zhiqiang,Mkhalid, Ibraheem A. I.,Thibault, Marie-Helene,Schwarz, Nicolle,Alcaraz, Gilles,Steffen, Andreas,Collings, Jonathan C.,Batsanov, Andrei S.,Howard, Judith A. K.,Marder, Todd B.
experimental part, p. 5022 - 5035 (2012/05/20)
An efficient synthetic route to 2-and 2,7-substituted pyrenes is described. The regiospecific direct C-H borylation of pyrene with an iridium-based catalyst, prepared in situ by the reaction of [{Ir(μ-OMe)cod}2] (cod=1,5-cyclooctadiene) with 4,4′-di-tert-butyl-2,2′-bipyridine, gives 2,7-bis(Bpin)pyrene (1) and 2-(Bpin)pyrene (2, pin=OCMe 2CMe2O). From 1, by simple derivatization strategies, we synthesized 2,7-bis(R)-pyrenes with R=BF3K (3), Br (4), OH (5), B(OH)2 (6), and OTf (7). Using these nominally nucleophilic and electrophilic derivatives as coupling partners in Suzuki-Miyaura, Sonogashira, and Buchwald-Hartwig cross-coupling reactions, we obtained 2,7-bis(R)-pyrenes with R=(4-CO2C8H17)C6H4 (8), Ph (9), Ca≡CPh (10), Ca≡C[{4-B(Mes)2}C 6H4] (11), Ca≡CTMS (12), Ca≡C[(4-NMe 2)C6H4] (14), Ca≡CH (15), N(Ph)[(4-OMe)C6H4] (16), and R=OTf, R′=Ca≡CTMS (13). Lithiation of 4, followed by reaction with CO2, yielded pyrene-2,7-dicarboxylic acid (17), whilst borylation of 2-tBu-pyrene gave 2-tBu-7-Bpin-pyrene (18) selectively. By similar routes (including Negishi cross-coupling reactions), monosubstituted 2-R-pyrenes with R=BF3K (19), Br (20), OH (21), B(OH)2 (22), [4-B(Mes)2]C 6H4 (23), B(Mes)2 (24), OTf (25), Ca≡CPh (26), Ca≡CTMS (27), (4-CO2Me)C6H4 (28), Ca≡CH (29), C3H6CO2Me (30), OC 3H6CO2Me (31), C3H 6CO2H (32), OC3H6CO2H (33), and O(CH2)12Br (34) were obtained from 2. These derivatives are of synthetic and photophysical interest because they contain donor, acceptor, and conjugated substituents. The crystal structures of compounds 4, 5, 7, 12, 18, 19, 21, 23, 26, and 28-31 have also been obtained from single-crystal X-ray diffraction data, revealing a diversity of packing modes, which are described in the Supporting Information. A detailed discussion of the structures of 1 and 2, their polymorphs, solvates, and co-crystals is reported separately. Copyright
