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901.
Takakusa H Kikuchi K Urano Y Sakamoto S Yamaguchi K Nagano T 《Journal of the American Chemical Society》2002,124(8):1653-1657
Ratiometric measurement is a technique that can provide precise data and even quantitative detection. To carry out ratiometric measurements, it is necessary that the sensor molecule exhibits a large shift in its emission or excitation spectrum after reaction with the target molecule. Fluorescence resonance energy transfer (FRET) is one mechanism used to obtain a large spectral shift. In this study, our aim was to develop a ratiometric fluorescent sensor molecule for phosphodiesterase activity based on FRET. We designed and synthesized CPF4 with a coumarin donor, a fluorescein acceptor, and two phenyl linkers having the phosphodiester moiety interposed between them. In the emission spectrum of CPF4 in aqueous buffer excited at 370 nm, the emission of the coumarin donor was strongly quenched and the emission of the fluorescein acceptor was observed. This emission spectrum demonstrates that energy transfer from the coumarin donor to the fluorescein acceptor proceeds efficiently. Addition of a phosphodiesterase to an aqueous solution of CPF4 resulted in an increase in the donor fluorescence and a decrease in the acceptor fluorescence. CPF4 exhibited a large shift in its emission spectrum after the hydrolysis of the phosphodiester group by the enzyme. This large shift of the emission spectrum indicates that ratiometric measurements can be made by using CPF4. The method described in this paper for designing enzyme-cleavable sensor molecules based on FRET should be readily applicable to other hydrolytic enzymes. 相似文献
902.
A convergent synthetic route to the (E)FGH ring system 4 of ciguatoxins, the causative toxins for ciguatera fish poisoning, has been developed. The synthesis features convergent coupling to form dioxane acetal, regioselective acetal cleavage by diethylaluminum phenylthiolate or diisobutylaluminum phenylselenolate followed by intramolecular radical cyclization to construct the oxepane ring G, and a ring-closing metathesis reaction to form the hexahydrooxonine ring F. The hexahydrooxonine ring F of tetracyclic model system 4 existed as a 5:1 equilibrium mixture of two conformers (UP and DOWN conformers), with the UP one predominating. This is the first illustration that reproduces the preference for the UP conformer over the DOWN one, which preference was observed for natural ciguatoxins. 相似文献
903.
Reaction of 2,4-dichlorothienopyrimidines and -quinazolines 1 with sodium borohydride gave the corresponding 2-chloro-3,4-dihydro derivatives 2. Some nucleophilic substitutions of 2b afforded 2-substituted derivatives 3b-7b and reaction of 2g,h with ethyl bromoacetate yielded selectively the corresponding 3-substituted compounds 8g,h which were derived to imidazo[2,1-b]quinazolin-2-ones 9g,h . 相似文献
904.
Tadashi Yamaguchi Fumie Yamazaki Tasuku Ito 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(4):m213-m214
(1,4,7‐Trithiacyclononane)silver trifluoromethanesulfonate crystallizes in a tetrameric form from nitromethane, to give the title compound, [Ag4(C6H12S3)4](CF3SO3)4·2CH3NO2. The complex cation consists of four [AgL]+ units (L is 1,4,7‐trithiacyclononane), with four Ag—S—Ag bridges forming a cyclic tetramer. The almost planar Ag4S4 ring takes an octagonal form. 相似文献
905.
Yoshida H Harada H Nakano Y Nohta H Ishida J Yamaguchi M 《Biomedical chromatography : BMC》2004,18(9):687-693
A liquid chromatographic method for highly sensitive and selective fluorometric determination of polyamines (putrescine, cadaverine, spermidine and spermine) in human urine is described. This method is based on an intramolecular excimer-forming fluorescence derivatization with a pyrene reagent, 4-(1-pyrene)butanoyl chloride (PBC), followed by reversed-phase liquid chromatography. The method offers higher sensitivity for determination of spermidine and spermine than previously reported method utilizing 4-(1-pyrene)butyric acid N-hydroxysuccinimide ester as a derivatization reagent. Samples containing free polyamines in diluted human urine were directly derivatized with PBC and separated on an octyl column. The derivatives were detected at excitation 345 and emission 475 nm wavelengths. For determination of total polyamine content, the conjugated polyamines were first hydrolyzed in 4 M HCl. The detection limits (signal-to-noise ratio = 3) for polyamines in urine were 1.1-3.4 pmol/mL. At optimized derivatization and chromatographic conditions, interferences such as biogenic monoamines gave no peaks or the peaks did not interfere with the peaks of polyamine derivatives. In conclusion, the present derivatization method allows direct determination of polyamines in human urine samples without the need for sample clean-up procedures. 相似文献
906.
Seiji Yamaguchi Masahide Kurosaki Keiko Orito Hajime Yokayama Yoshiro Hirai Shunsaku Shiotani 《Journal of heterocyclic chemistry》1998,35(6):1237-1247
Bromination of 2-methylfuropyridines 1a-d-Me gave the 3-bromo derivatives 2a-d , while the 2-cyano compounds 1a-d-CN resulted in the recovery of the starting compounds. Nitration of 1a-d-Me and 1a-d-CN did not yield the corresponding nitro derivative, except for 1-c-CN giving 3-nitro derivative 3c in 7% yield. N-Oxidation of 1a-d-Me and 1b-d-CN with m-chloroperbenzoic acid yielded the N-oxides 4a-d-Me and 4b-d-CN , whereas 1a-CN did not afford the N-oxide. Cyanation of N-oxides 4a-d-Me and 4b-d-CN with trimethylsilyl cyanide gave the corresponding α-cyanopyridine compounds 5a-d-Me and 5b-d-CN . Chlorination of 4a-d-Me and 4b-d-CN with phosphorus oxychloride also gave the α-chloropyridine compounds 6b-d-Me and 6b-d-CN , accompanying formation of γ-chloropyridine 6a-Me, 6′b-Me and 6′b-CN , β-chloropyridine 6′b-CN , and α'-chloropyridine derivatives 6′c-Me and 6′c-CN . Acetoxylation of 4a-d-Me and 4b-d-CN with acetic anhydride yielded α-acetoxypyridine compounds 7a-Me and 7b-CN , pyridone compounds 11d-Me, 11c-CN and 11d-CN , 3-acetoxy compounds 8, 9b, 9c , and 2-acetoxymethyl derivatives 10b and 10c. 相似文献
907.
Rimiko Oguchi Ayako Shimizu Satoru Yamashita Kenji Yamaguchi Philip Wylie 《Journal of separation science》1991,14(6):412-416
Volatile pyrolysates of a methyl methacrylate-butadiene-styrene copolymer (MBS) have been analyzed using a capillary gas chromatograph equipped with a Fourier transform infrared detector in tandem with a mass selective detector, and a gas chromatograph-atomic emission detector system. Among the volatile compounds observed were monomers used for synthesis of the polymer. Numerous oligomers of higher boiling point were also found; identification of these could be used to give structural information about the parent polymer. Combining information from these techniques was found to be extremely useful for the analysis of polymer pyrolysis products. In characterizing each compound it was found particularly helpful to juxtapose feature-specific chromatograms (e.g., single ion monitoring from the mass-selective detector and the selected wavelength chromatography from the infrared detector). 相似文献
908.
Kamata J Okada T Kotake Y Niijima J Nakamura K Uenaka T Yamaguchi A Tsukahara K Nagasu T Koyanagi N Kitoh K Yoshimatsu K Yoshino H Sugumi H 《Chemical & pharmaceutical bulletin》2004,52(9):1071-1081
As part of a series of studies to discover new topoisomerase II inhibitors, novel pyrimidoacridones, pyrimidophenoxadines, and pyrimidocarbazoles were synthesized, and in vitro and in vivo antitumor activities and DNA-protein and/or DNA-topoisomerase II cross-linking activity as an indicator of topoisomerase II-DNA cleavable complex formation were evaluated. The pyrimidocarbazoles possessed high in vitro and in vivo potencies. Compound 26 (ER-37326), 8-acetyl-2-[2-(dimethylamino)ethyl]-1H-pyrimido[5,6,1-jk]carbazole-1,3(2H)-dione, showed in vitro growth inhibitory activity with respective IC(50) values of 0.049 microM and 0.35 microM against mouse leukemia P388 and human oral cancer KB. In vivo, this compound inhibited the tumor growth of mouse sarcoma M5076 implanted into mice with T/C values of 42% and 13% at 3.13 and 6.25 mg/kg/d respectively without significantly affecting the body weight. In addition, compound 26 (ER-37326) increased the formation of DNA-topoisomerase II cross-linking in P388 cells. 相似文献
909.
ZrO2酸碱性质的TPD表征 I. 单组分吸附研究 总被引:2,自引:3,他引:2
以NH_3、吡啶、Et_3N、CO_2和苯酚为探针,用TPD-MS方法对ZrO_2催化剂的酸碱性质进行了表征.ZrO_2上碱性探针(NH_3、吡啶和Et_3N)的脱附温度远低于在强酸性SiO_2-Al_2O_3上;而酸性探针CO_2的脱附温度远低于在强碱性MgO上的结果.为ZrO_2的弱酸弱碱性质提供了证明.NH_3吸附IR结果表明ZrO_2表面配位不饱合Zr~(4+)为酸(Lewis酸)中心.NH_3、吡啶和Et_3N与这些酸中心作用的方式和能量分布相似.NH_3和CO_2的TPD谱图均存在三个脱附峰,且相应脱附峰的温度范围相近.表明ZrO_2的酸中心和碱中心具有匹配相当的酸、碱强度,ZrO_2为典型的酸-碱双功能催化剂,在苯酚的TPD过程中,ZrO_2的特征表现为对苯酚的强吸附和对苯酚分解的高活性.文中结合IR结果,对与NH_3和CO_2的脱附相联系的表面吸附物种分别进行了讨论. 相似文献
910.
Takayuki Otsu Shuzo Aoki Masato Nishimura Masami Yamaguchi Yoshihiro Kusuki 《Journal of polymer science. Part A, Polymer chemistry》1969,7(12):3269-3277
The polymerizations of methyl methacrylate, styrene, and isobutyl vinyl ether with the binary systems of reduced nickel and chlorosilanes [(CH3)nSiCl4?n, n = 0–3] have been investigated. It was found that these systems could act as both radical and cationic initiators, depending on the nature of vinyl monomers used. The kinetic investigations indicated that methyl methacrylate polymerized via a radical mechanism, and the initiating activity of chlorosilanes decreased in the following order: SiCl4 > CH3SiCl3 > (CH3)2SiCl2 > (CH3)3SiCl ? 0. Cationic initiations were observed in the polymerizations of styrene and isobutyl vinyl ether. In the latter case, the activity of chlorosilanes was in the following order: (CH3)3SiCl > (CH3)2SiCl2 > CH3SiCl3 ? SiCl4. From the results obtained, a possible mechanism of selective initiation with these systems is proposed and discussed. 相似文献