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61.
Bolaamphiphilic tetraresorcinolporphyrins with eight long side chains (octopusporphyrins) and their metal complexes form monolayered assemblies in bulk aqueous solution. The nano-structure, the photoinduced electron transfers and the O2 coordination of these octopusporphyrin assemblies are described. In the micellar fibers of 1a and 1b, a unique spherical arrangement of eight methyl groups on both sides of the porphyrin ring plane provides hydrophobic porphyrin centers which align in a string of pearls. Exciton calculations indicated a tilt stacking porphyrins arrangement with a separation of 11 Å. These fibers fluoresced strongly; electron transfer reaction was therefore observed between the porphyrin center and hydrophobic quenchers as well as hydrophilic quenchers. The fibers were also active as photocatalysts in the reduction of dimethylviologen by triethanolamine. Octopusporphyrins with different metal centers can also produce fibrous aggregates, for example, H2P/Zn(II)P and Zn(II)P/Fe(III)P couples. The fluorescence quenching of Zn(II)P in the Zn(II)P/Fe(III)P hybrid fibers can be ascribed to the intermolecular electron transfer within the fibers. In H2P/Zn(II)P couple, excitation energy transfer from excited Zn1*P to H2P occurred after photoexcitation. Octopusporphyrin with four dialkylglycerophosphocholine groups on both sides of the ring plane ( 2b ) forms spherical unilamellar vesicles. Based on cryomicroscopy, a white line was observed with a diameter of 15 Å in the middle of the membrane which are obviously a porphyrin layer with low molecular packing. The octopusheme ( 2c ) vesicles prepared in a similar manner with 20-fold excess molar coexistence of 1-dodecyl-2-methylimidazole (DMIm) can bind and release oxygen reversibly at 25°C. Moreover, water-soluble octopusporphyrin ( 3a ) produced fluorescent and non-fluorescent monolayer assemblies by anion exchange of the head groups, e.g. 3a with sodium perchlorate showed planar sheets. An exciton calculation is consistent with a two-dimensional arrangement with porphyrin separations of 25.6 and 17.4 Å in the x- and y-directions, respectively. External addition of negatively charged electron acceptors, naphtoquinone sulfonate and anthraquinone sulfonate, led to partial quenching of the fluorescence of the central porphyrin layer. The results have been evaluated using equations derived for this special quenching. © 1998 John Wiley & Sons, Ltd. 相似文献
62.
Structural evolution of the solution of tetraethoxysilane hydrolyzed with [H2O]/[Si(OC2H5)4] = 2 under acidic condition has been investigated by rheological measurements. It was found that the solution behaves as a Newtonian liquid up to a highly viscous state and shows spinnability before gelation when the evaporation of the solvent is allowed during gelation reaction. On the other hand, the solution behaved as a non-Newtonian liquid in the viscous state, showing no spinnability when the evaporation of the solvent was not allowed during the reaction. It was indicated from the Casson plots that the spinnable solution prepared in the open system has no yield stress up to highly viscous states, whereas the non-spinnable solution prepared in the closed system has a yield stress at viscous states. It was proposed that the increase in viscosity of the open system solution is attributable to the concentration of the sol particles whereas that of the closed system solution is attributable to the formation of the three dimensional network in the solution. 相似文献
63.
A Cell‐Targeted Non‐Cytotoxic Fluorescent Nanogel Thermometer Created with an Imidazolium‐Containing Cationic Radical Initiator 下载免费PDF全文
Dr. Seiichi Uchiyama Dr. Toshikazu Tsuji Kyoko Kawamoto Dr. Kentaro Okano Eiko Fukatsu Takahiro Noro Kumiko Ikado Sayuri Yamada Yuka Shibata Dr. Teruyuki Hayashi Dr. Noriko Inada Dr. Masaru Kato Dr. Hideki Koizumi Prof. Hidetoshi Tokuyama 《Angewandte Chemie (International ed. in English)》2018,57(19):5413-5417
A cationic fluorescent nanogel thermometer based on thermo‐responsive N‐isopropylacrylamide and environment‐sensitive benzothiadiazole was developed with a new azo compound bearing imidazolium rings as the first cationic radical initiator. This cationic fluorescent nanogel thermometer showed an excellent ability to enter live mammalian cells in a short incubation period (10 min), a high sensitivity to temperature variations in live cells (temperature resolution of 0.02–0.84 °C in the range 20–40 °C), and remarkable non‐cytotoxicity, which permitted ordinary cell proliferation and even differentiation of primary cultured cells. 相似文献
64.
Kinetic experiments have been carried out on the reactions of isoquinoline N-oxide with p-toluenesulfonyl and other substituted benzenesulfonyl chlorides, varying solvent and salt compositions. The rate was correlated by the second-order equation, i.e., v = [N → O] × [ArSO2Cl], and was found to be accelerated in polar media. The addition of chloride ion was found to increase the rate considerably, while the rates of the over-all reaction became greater with arenesulfonyl chlorides bearing stronger electron-withdrawing substituents ( = +2·0). By the use of 1-deuterated isoquinoline N-oxide a small kinetic isotope effect (kH/kD = 1·2) was observed for this reaction. Based on these kinetic observations the rate-determining step of this reaction is considered to be the cleavage of N---O bond. Meanwhile, from the 18O-tracer experiments in several solvents using uniformly 18O-labelled p-toluenesulfonyl or p-bromobenzenesulfonyl chloride the migration of arenesulfonate was found to proceed mainly via oxygen-bridged ion pair pathway. 相似文献
65.
Jun-Ichi Matsumoto Teruyuki Miyamoto Akira Minamida Yoshiro Nishimura Hiroshi Egawa Haruki Nishimura 《Journal of heterocyclic chemistry》1984,21(3):673-679
Fluorination of the 2,6-disubstituted 3-aminopyridines 5 and 12 by the Balz-Schiemann reaction is described. 2,6-Dichloro-3-pyridinediazonium tetrafluoroborate ( 6 ) and 2-substituted 6-acetylamino-3-pyridinediazonium tetrafluoroborates 13 were heated with or without a solvent to give the corresponding fluorinated pyridines 7 and 14 , respectively, in good yields. 2-Substituted 6-acetylamino-3-fluoropyridines ( 14 ) were converted by a known method into a series of 7-substituted 1-ethyl-6-fluoro-1,4-dihydro-4-oxo-1,8-naphthyridine-3-carboxylic acids 21 including enoxacin [1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-1,8-naphthyridine-3-carboxylic acid [( 2 )], a new potential antibacterial agent. 相似文献
66.
In continuation of the study on the murexide reaction of caffeine with 3% hydrogen peroxide/hydrochloric acid and then with ammonia giving a purple coloration, we investigated the oxidation reaction of caffeine with 6% hydrogen peroxide/hydrochloric acid to isolate ten reaction products, 3-hydroxy-4,6-dimethyloxazolo[4,5-d]pyrimidine-2,5,7(3H,4H,6H)-trione 1 , 1,3-dimethylalloxan 2 , murexoin 3 , 1,3,7-trimethyl-2,6,8-trioxo-9-hydroxy-1H,3H,7H-xanthine 5 , 1,3,7-trimethyl-2,6,8-trioxo-1H,3H,7H-xanthine 6 , 1,3,7-trimethyl-2,6-dioxo-8-chloro-1H,3H,7H-xanthine 7, 5-(1,3-dimethyl-1,2,3,4,5,6-hexahydro-2,4,6-trioxopyrimidin-5-yl)-aminomethylene-1,3-dimethyl-1,2,3,4,5,6-hexahydro-2,4,6-trioxopyrimidine ammonium salt 9 , 1,3-dimethylpalabanic acid 10 , 1-methyl-2,4,5-trioxoimidazole 11 , 3-hydroxy-5,7-dimethyloxazolo[5,4-d]pyrimidine-2,4,6(3H,5H,7H)-trione 12 and 4,6,8-trimethyl-1,2,4-dioxazino[6,5-d]pyrimidine-3,5,7(4H,6H,8H)-trione 13 . The oxidation reaction using 6% hydrogen peroxide/hydrochloric acid was found to produce a similar purple coloration to that of the murexide reaction despite no subsequent addition of ammonia, indicating the liberation of ammonia by the oxidation of caffeine. Among the above compounds, the purple colored substance murexoin 3 and the yellow colored compound 9 were both ammonium salts, and compound 5 was the red colored substance. In the present investigation, these three compounds were found to contribute to the coloration. 相似文献
67.
T Konoshima M Kokumai M Kozuka M Iinuma M Mizuno T Tanaka H Tokuda H Nishino A Iwashima 《Chemical & pharmaceutical bulletin》1992,40(2):531-533
To search for possible anti-tumor-promoters, fourteen flavones obtained from the root of Scutellaria baicalensis were examined for their inhibitory effects on the Epstein-Barr virus early antigen (EBV-EA) activation by a short-term in vitro assay. Among these flavones, 5,7,2'-trihydroxy- and 5,7,2',3'-tetrahydroxyflavone showed remarkable inhibitory effects on the EBV-EA activation, and the effect of the latter on Raji cell cycle was also examined by flow cytometer. These two flavones exhibited remarkable inhibitory effects on mouse skin tumor promotion in an in vivo two-stage carcinogenesis test. 相似文献
68.
Teruyuki Nakato Yumiko Iwata Kuzuyuki Kuroda Chuzo Kato 《Journal of inclusion phenomena and macrocyclic chemistry》1992,13(3):249-256
Intercalation of methylene blue into layered titanic acid H2Ti4O9 was examined by a guest exchange method using a propylammonium-H
x
Ti4O9 intercalation compound as the intermediate. Methylene blue cations were arranged in the interlayer space obliquely to the layer surface. The visible spectrum of the intercalation compound suggested that the methylene blue cations were in an associated state in the interlayer space of H2Ti409. The intercalated methylene blue cations underwent a reversible electrochemical redox reaction in the dark, indicating that intercalation compounds of H2Ti4O9 can be applied to a modified electrode. 相似文献
69.
70.
The simple one-pot reaction of protoporphyrin IX and omega-(N-imidazolyl)alkylamine or O-methyl-L-histidyl-glycine with benzotriazol-1-yl-oxytris(dimethylamino)phosphonium hexafluorophosphate at room temperature produced a series of protoporphyrin IX species with a covalently linked proximal base at the propionate side-chain. The central iron was inserted by the general FeCl2 method, converting the free-base porphyrins to the corresponding protoheme IX derivatives. Mesoporphyrin IX and diacetyldeuteroporphyrin IX analogues were also prepared by the same procedure. The Fe(II) complexes formed dioxygen (O2) adducts in dimethylformamide at 25 degrees C. Some of them were incorporated into the hydrophobic domain of recombinant human serum albumin (rHSA), providing albumin-heme hybrids (rHSA-heme), which can bind and release O2 in aqueous media (pH 7.3, 25 degrees C). The oxidation process of converting the dioxygenated heme in rHSA to the inactive Fe(III) state obeyed first-order kinetics, indicating that the mu-oxo dimer formation was prevented by the immobilization of heme in the albumin scaffold. The rHSA-heme, in which the histidylglycil tail coordinates to the Fe(II) center, showed the most stable O2 adduct complexes. 相似文献