- Synthesis method of arylimidazophenanthroline fluorescence dye, and recognition of metal ions
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The invention discloses a synthesis method of an arylimidazophenanthroline fluorescence dye, and recognition of metal ions. The synthesis method is a method for synthesizing arylimidazo[4,5-f]phenanthroline oxa-crown ether compounds from cheap and easily available 1,10-phenanthroline through a series of steps. Fluorescence properties of the arylimidazo[4,5-f]phenanthroline compounds are screened,the complexing property of the compounds and metal ions is verified through screening experiments of different metal ions and experiments of ion concentration and the like, and recognition of the metal ions Zn in tumor cells is achieved. The fluorescence probe has the following technical effects: 1, the compounds respectively have high selectivity to Zn Zn on wide metal ions; and 2, a fluorescence quenching molecular switch responding to Zn can be obtained in MCF-7 cells, and lays a great foundation for the application of the system in fields of biological recognition and the like.
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Paragraph 0012
(2020/02/20)
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- THIENODIAZEPINE DERIVATIVES AND APPLICATION THEREOF
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The present invention relates to a class of thienodiazepine derivatives and an application thereof in the preparation of a drug for the treatment of diseases associated with bromodomain and extra-terminal (BET) Bromodomain inhibitors. Specifically, the present invention relates to compounds represented by formulas (I) and (II), as well as pharmaceutically acceptable salts thereof.
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Paragraph 0301; 0304-0305
(2020/08/09)
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- SUBSTITUTED PYRIMIDINES, PHARMACEUTICAL COMPOSITIONS AND THERAPEUTIC METHODS THEREOF
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The invention provide novel pyrimidine derivatives and analogs having inhibitory activities towards certain tyrosine kinases, e.g., Bruton's tyrosine kinase (Btk) and/or Focal adhesion kinase (FAK), extracellular signal-regulated kinase (ERK), pharmaceutical compositions thereof, and methods of treatment, reduction or prevention of certain diseases or conditions mediated by such by tyrosine kinases, e.g., cancers, tumors, fibrosis, inflammatory diseases, autoimmune diseases, diabetes, or immunologically mediated diseases.
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Paragraph 00233
(2019/03/17)
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- Preparation, photophysical, electrochemical, and ion-binding properties of Ru(II) polypyridyl complexes containing a crown ether unit
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Two polypyridyl ligands, 4'-(4,5-diazafluoren-9-ylimino)benzo-15-crown-5 (L1) and 4'-(4,5-diazafluoren-9-ylimino)benzo-12-crown-4 (L 2), and their Ru(II) complexes [(bpy)2RuL](PF 6)2 and [(bpy)2RuL2](PF 6)2, respectively, have been synthesized and characterized. The two complexes display metal-to-ligand charge transfer absorptions at around 444 nm in CH3CN solution at r. t. and emission at around 573 nm in an EtOH-MeOH (4:1, v/v) glassy matrix at 77 K. Electrochemical studies of the complexes show one Ru(II)-centered oxidation at around 1.33 V and three ligandcentered reductions. The binding ability of the complexes with Na+ and Li+ has been investigated by UV/Vis absorption and emission spectroscopy and electrochemical titrations. Addition of Na+ and Li+ to solutions of the complexes results in a progressive quenching of the emission, a hyperchromic effect of the UV/Vis absorption, and a progressive cathodal shift of the Ru(II)-centered E 1/2 potential. The stability constants for the stoichiometric 1:1 ratio of the complexes and the cations have been obtained by UV/Vis absorption titration.
- Cheng, Feixiang,Tang, Ning,Chen, Jishu,Wang, Fan,Chen, Longhai
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scheme or table
p. 923 - 929
(2011/10/11)
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- Two new "onium" fluorosilicates, the products of interaction of fluorosilicic acid with 12-membered macrocycles: Structures and spectroscopic properties
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Two novel compounds, (L1H)2[SiF6] ·2H2O (1) and (L2H)2[SiF 5(H2O)]2·3H2O (2), resulting from the reactions of H2SiF6 with 4′-aminobenzo-12- crown-4 (L1) and monoaza-12-crown-4 (L2), respectively, were studied by X-ray diffraction and characterised by IR and 19F NMR spectroscopic methods. Both complexes have ionic structures due to the proton transfer from the fluorosilicic acid to the primary amine group in L1 and secondary amine group incorporated into the macrocycle L2. The structure of 1 is composed of [SiF6]2- centrosymmetric anions, N-protonated cations (L1H)+, and two water molecules, all components being bound in the layer through a system of NH...F, NH...O and OH...F hydrogen bonds. The [SiF 6]2- anions and water molecules are assembled into inorganic negatively-charged layers via OH...F hydrogen bonds. The structure of 2 is a rare example of stabilisation of the complex anion [SiF 5(H2O)]-, the labile product of hydrolytic transformations of the [SiF6]2- anion in an aqueous solution. The components of 2, i.e., [SiF5(H2O)] -, (L2H)+, and water molecules, are linked by a system of NH...F, NH...O, OH...F, OH...O hydrogen bonds. In a way similar to 1, the [SiF5(H2O)]- anions and water molecules in 2 are combined into an inorganic negatively-charged layer through OH...F and OH...O interactions. The Royal Society of Chemistry.
- Gelmboldt, Vladimir O.,Ganin, Eduard V.,Fonari, Marina S.,Simonov, Yurii A.,Koroeva, Larisa V.,Ennan, Alim A.,Basok, Stepan S.,Shova, Sergiu,Kaehlig, Hanspeter,Arion, Vladimir B.,Keppler, Bernhard K.
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p. 2915 - 2924
(2008/02/10)
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- Supramolecular crown ether probe/γ-cyclodextrin complex sensors for alkali metal ion recognition in water
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Crown ether probes C3-12C4 and C3-18C6, in which the pyrenyl moieties as fluorophore and benzo-12-crown-4 or benzo-18-crown-6 acting as ion recognition sites are connected by a trimethylene spacer, have been synthesized. Their supramolecular function for alkali metal ion sensing in water is compared with that of the previously designed C3-15C5/γ-CyD complex sensor. The C3-12C4, C3-15C5, and C3-18C6 are found to selectively form 2:1 complexes with Na+, K+, and Cs+, respectively, in the presence of γ-CyD and to exhibit pyrene dimer emission in water. These results demonstrate that the selectivity of the crown ether probe/γ-CyD complexes can be tuned by simply altering their crown ether ring size. The apparent 2:1 binding constants of the probes with alkali metal ions are determined at the optimum γ-CyD concentrations for each probe. For C3-12C4/γ-CyD complex, the accurate binding constant could not be obtained due to the relatively large deviation for the response. However, the fitting curve reveals that the binding constant is about 107 M-2. The 2:1 binding constants of the C3-15C5/γ-CyD complex for K+ and C3-18C6/γ-CyD complex for Cs+ are (3.8 ± 1.3) x 109 M-2 and (5.8 ± 4.6) x 107 M-2, respectively. These values are considerably larger than those of the corresponding benzocrown ethers in organic solvents. In the suparamolecular sensing system, the dimer formation of the probes inside the γ-CyD is selectively promoted by alkali metal ion binding in water. This is a novel sensing mechanism in which the dynamic molecular recognition events are successfully utilized for ion sensing in water.
- Yamauchi, Akiyo,Hayashita, Takashi,Kato, Ayako,Teramae, Norio
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p. 1527 - 1532
(2007/10/03)
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- Nitration of benzo crown ethers with potassium nitrate in polyphosphoric acid
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A general method for the nitration of benzo crown ethers with potassium nitrate in polyphosphoric acid has been developed. Mono- and dinitro derivatives of benzo-12-crown-4, benzo-15-crown-5, dibenzo-18-crown-6, and dibenzo-24-crown-8 have been prepared. The role of complex formation in the regioselective tendency for the nitration of dibenzo-18-crown-6 has been demonstrated.
- Grebenyuk,Andreev,Stempnevskaya,Levkovich,Tashmukhamedova
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p. 1449 - 1456
(2007/10/03)
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- Highly preorganized bis(benzocrown ether)s for the binding of metal ions
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Several bis(crown ethers)s consisting of benzo-12-crown-4, benzo-15-crown-5, and benzo-18-crown-6, were prepared and their complexation properties with Na+ and K+ were determined by the liquid-liquid extraction method. The remarkable 'biscrown effect' was observed in the extractions of both Na+ and K+ using bis(benzo-12-crown-4) and bis(benzo-15-crown-5). Unsymmetrical bis(crown ether)s also exhibit much higher extractabilities of both Na+ and K+ than the corresponding mono(benzocrown ether)s.
- Jeong, Kyu-Sung,Pyun, Seung Yup
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p. 7041 - 7044
(2007/10/02)
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- 13-AMINO-1,4,7,10-BENZOTETRAOXA-15-CYCLODODECENE
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A separation was performed for benzo-12-crown-4 and dibenzo-24-crown-8 obtained as a mixture by the reaction of pyrocatechol with 1,8-dichloro-3,6-dioxaoctane.Nitro and amino derivatives of benzo-12-crown-4 were obtained.
- Markovich, I. S.,Filyagina, N. A.,Blokhina, L. I.,Dziomko, V. M.,Poponova, R. V.,et al.
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p. 147 - 148
(2007/10/02)
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- Photoresponsive Crown Ethers. 4. Influence of Alkali Metal Cations on Photoisomerization and Thermal Izomerization of Azobis(benzocrown ether)s
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Five photoresponsive azobis(benzocrown ether)s 1(4,4), 1(5,5), 1(6,6), 2(5,5) and 2(6,6), were synthesized, where numbers in parentheses denote the number of oxygens in benzocrown ethers, and crown series 2 have two tert-butyl groups in the 2 and 2' position of the azo linkage.We have found that (i) in the presence of alkali metal cations, the concentration of cis isomers (cis percent) under the photostationary state is enhanced and the rate of thermal cis-to-trans isomerization (k) is supressed, the optima cis-1(5,5) and cis-1(6,6) being observed for Rb+ and Cs+, respectively, (ii) Rb+ and Cs+ are extracted most efficiently from an aqueous solution to an organic phase (o-dichlorobenzene) with cis-1(5,5) and cis-1(6,6), respectively, (iii) cis percent and k of 2(5,5) and 2(6,6) are affected by alkyli metal cations smaller than those of corresponding 1(5,5) and 1(6,6), and (iv) cis percent and k of 1(4,4) are less affected by added alkali metal cations and the extractability is very low.The increase in cis percent and the supression of the thermal isomerization rate are rationalized in terms of the "tying effect" of complexed cations requiring the additional energy to disrupt the crown-cation interaction.The correlation of the extractability with cis percent and k implies that alkali metal cations are extracted under photoirradiation as intramolecular 1:2 cation/crown complexes and the ion selectivity is associated with the fitness between the ion size and the size of the spatial cavity provided by two crown ethers of cis form.The ion selectivity suggests (i) the cavity size of cis-1(6,6) is greater than that of cis-(5,5) and (ii) the cavity sizes of crown series 2 are smaller than those of crown series 1 probably owing to the steric repulsion of the tert-butyl groups.Hence, the ion selectivity in the photocontrolled solvent extraction is effected by the crown ring size and the steric crowding around the azo linkage.
- Shinkai, Seiji,Ogawa, Toshiyuki,Kusano, Yumiko,Manabe, Osamu,Kikukawa, Kiyoshi,et al.
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p. 1960 - 1967
(2007/10/02)
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