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31.
Komatsu H Citterio D Fujiwara Y Minamihashi K Araki Y Hagiwara M Suzuki K 《Organic letters》2005,7(14):2857-2859
[structure: see text] The jewel pendant ligand has multiple chromogenic units combined in a single molecule with the dyes linked to a semiselective binding site by three heteroatoms (O, N, S) having different HSAB characteristics, to indicate diverse response to individual transition metal ions. Using a single-molecular multianalyte sensor, multiple analytes could be determined with a minimal sensing system. 相似文献
32.
Masaki Hasegawa Kazuhiko Saigo Hirokazu Katsuki Noriyuki Yonezawa Toshio Kanoe 《Journal of polymer science. Part A, Polymer chemistry》1983,21(8):2345-2362
The ring-opening polyaddition reaction of anti and syn head-to-head Coumarin dimers with diamines and the photocleavage behavior of the resulting polyamides were investigated. Anti head-to-head Coumarin dimer successfully reacted with aliphatic and aromatic diamines in an aprotic polar solvent to give corresponding high molecular weight polyamides. The polyamides showed good film forming ability and exhibited solubility behavior typical of polyelectrolytes. Furthermore, these polyamides were found to undergo exclusively asymmetric photocleavage on the cyclobutane rings in the polymer main chain to give a fumaramide unit with elimination of 2,2′-dihydroxystilbene. On the other hand, syn head-to-head Coumarin dimer gave only low molecular weight polyamides. These polymerization and photocleavage behaviors were elucidated in comparison with those of model reactions. 相似文献
33.
Fischer indolization of ethyl pyruvate 2-methoxyphenylhydrazone (1) with p-toluene-sulfonic acid in benzene in the presence of an enolizable dicarbonyl or an indolic compound gave either an indole product having an active methine group at C6 or a novel type of 3,6′-biindole compound. Structures of the products were established by NMR spectra and chemical evidence. 相似文献
34.
Khademhosseini A Yeh J Eng G Karp J Kaji H Borenstein J Farokhzad OC Langer R 《Lab on a chip》2005,5(12):1380-1386
We present a soft lithographic method to fabricate multiphenotype cell arrays by capturing cells within an array of reversibly sealed microfluidic channels. The technique uses reversible sealing of elastomeric polydimethylsiloxane (PDMS) molds on surfaces to sequentially deliver various fluids or cells onto specific locations on a substrate. Microwells on the substrate were used to capture and immobilize cells within low shear stress regions inside channels. By using an array of channels it was possible to deposit multiple cell types, such as hepatocytes, fibroblasts, and embryonic stem cells, on the substrates. Upon formation of the cell arrays on the substrate, the PDMS mold could be removed, generating a multiphenotype array of cells. In addition, the orthogonal alignment and subsequent attachment of a secondary array of channels on the patterned substrates could be used to deliver fluids to the patterned cells. The ability to position many cell types on particular regions within a two dimensional substrate could potentially lead to improved high-throughput methods applicable to drug screening and tissue engineering. 相似文献
35.
Otaka A Yukimasa A Watanabe J Sasaki Y Oishi S Tamamura H Fujii N 《Chemical communications (Cambridge, England)》2003,(15):1834-1835
Gamma-acetoxy-alpha,beta-enoates were easily reduced by samarium diiodide (SmI2) in THF to generate samarium dienolates which were kinetically trapped with ease at their alpha-positions by electrophiles (proton, aldehydes or ketones) to yield (E)-alkene dipeptide isosteres or gamma-amino acid derivatives in high chemical yields. 相似文献
36.
Isotachophoresis carried out in a 0.25 mm i.d. fused-silica capillary tube yielded high resolution, compared with that in a fluorinated ethylene-propylene polymer tube. The use of an ultraviolet-visible multichannel spectrophotometer with photodiode array as detector together with a cross flow cell (volume 0.01 μl) was investigated. The system was successfully applied to the analysis of cationic dyes such as neutral red, bismarck brown, and basic fuchsine. 相似文献
37.
In the reaction of soybean lipoxygenase (EC 1.13.11.12) with polyunsaturated fatty acids such as linoleic, linolenic and arachidonic acids, some radical species were detected using the electron spin resonance (ESR) spin-trapping technique. The radical species derived from the three polyunsaturated fatty acids were not distinguishable because the ESR spectra of the spin adducts of nitrosobenzene with their three radical species showed no difference in their hyperfine splittings. To overcome this defect of the spin-trapping technique, these spin-adducts were separated by employing high-performance liquid chromatography (HPLC) combined with ESR spectroscopy. The spin adducts were eluted from a C18 reversed-phase column in the order linolenic acid, linoleic acid and arachidonic acid. The half-lives of the spin adducts separated by HPLC-ESR were determined as linoleic acid 600 min, linolenic acid 360 min and arachidonic acid 160 min. The use of an ultraviolet detector together with the HPLC-ESR technique resulted in a 500-fold increase in sensitivity in the detection of the radical species. 相似文献
38.
The intercalation of 4-phenylazoaniline (PAA) in supercritical carbon dioxide (SC-CO(2)) into montmorillonite (TMA-Mnt) pillared with tetramethylammonium ions at 313 K and 15 MPa was investigated. The adsorption rate and equilibrium PAA uptake were compared with those in n-hexane, CCl(4) and benzene solutions at 313 K. The XRD and N(2) adsorption/desorption analyses showed that TMA-Mnt after adsorption of PAA in SC-CO(2) had the same pore structure as after adsorption of PAA in normal solvents. SC-CO(2) was found to be a good medium for PAA adsorption owing to its having a relatively high adsorption rate and the highest adsorptivity at the same PAA concentration. The properties of PAA adsorption on TMA-Mnt could be well elucidated by the difference in solubility parameters between liquid and solid phases. 相似文献
39.
Otaka A Watanabe J Yukimasa A Sasaki Y Watanabe H Kinoshita T Oishi S Tamamura H Fujii N 《The Journal of organic chemistry》2004,69(5):1634-1645
A samarium diiodide (SmI(2))-mediated reduction of gamma,gamma-difluoro-alpha,beta-enoates (15, 29, and 34) was successfully applied to the synthesis of (Z)-fluoroalkene dipeptide isosteres (23, 30, and 35), which have served as potential dipeptide mimetics. Reduction of the gamma,gamma-difluoro-alpha,beta-enoates by SmI(2) proceeded via successive two-electron transfers to form dienolate species which upon kinetically controlled trapping with t-BuOH yielded Xaa-Gly-type fluoroalkene isosteres exemplified by 23, 30, and 35. Replacement of the t-BuOH kinetic trapping agent with aldehydes or ketones provided access to alpha-substituted fluoroalkene isosteres (43 and 45) through aldol reactions of Sm-dienolates with the carbonyl compounds. Of particular note, the use of the SmI(2)-HCHO reagent system with chiral enoate 34 provided D-Phe-psi[(Z)-CF[double bond]CH]-D/L-Ser isosteres (45), which could be converted to enantiomerically pure isosteres (49-52) that bore a variety of side chain functionalities at the alpha-position. This was achieved by a sequence of manipulations consisting of beta-lactone formation followed by chromatographic separation and ring-opening with soft nucleophiles. Included in the present work is the first utilization of a Rh-catalyzed Reformatsky reaction of chiral imines for the stereoselective preparation of alpha,alpha-difluoro-beta-amino acid derivatives (28 and 33). The appropriate choice of reagents (carbonyl compounds for kinetic trapping or ring-opening nucleophiles and imines for Reformatsky reactions) allows the presented methodology to yield various fluoroalkene isosteres possessing a wide range of side chain functionalities. 相似文献
40.
Komatsu H Iwasawa N Citterio D Suzuki Y Kubota T Tokuno K Kitamura Y Oka K Suzuki K 《Journal of the American Chemical Society》2004,126(50):16353-16360
The role of intracellular magnesium ions is of high interest in the fields of pharmacology and cellular biology. To accomplish the dynamic and three-dimensional imaging of intracellular Mg2+, there is a strong desire for the development of optimized Mg2+ fluorescent probes. In this paper we describe the design, synthesis, and cellular application of the three novel Mg2+ fluorescent probes KMG-101, -103, and -104. The compounds of this series feature a charged beta-diketone as a binding site specific for Mg2+ and a fluorescein residue as the fluorophore that can be excited with an Ar+ laser such as is widely used in confocal scanning microscopy. This molecular design leads to an intensive off-on-type fluorescent response toward Mg2+ ions. The two fluorescent probes KMG-103 and -104 showed suitable dissociation constants (Kd,Mg2+ = 2 mM) and nearly a 10-fold fluorescence enhancement over the intracellular magnesium ion concentration range (0.1-6 mM), allowing high-contrast, sensitive, and selective Mg2+ measurements. For intracellular applications, the membrane-permeable probe KMG-104AM was synthesized and successfully incorporated into PC12 cells. Upon application of the mitochondria uncoupler FCCP to the probe-incorporated cells, the resulting increase in the free magnesium ion concentration could be followed over time. By using a confocal microscope, the intracellular 3D magnesium ion concentration distributions were satisfactorily observed. 相似文献