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41.
The pyridinium bisretinoid A2E, an autofluorescent pigment that accumulates in retinal pigment epithelial cells with age and in some retinal disorders, can mediate a detergent-like perturbation of cell membranes and light-induced damage to the cell. The photodynamic events initiated by the sensitization of A2E include the generation of singlet oxygen and the oxidation of A2E at carbon-carbon double bonds. To assess the ability of plant-derived anthocyanins to modulate adverse effects of A2E accumulation on retinal pigment epithelium (RPE) cells, these flavylium salts were isolated from extracts of bilberry. Nine anthocyanin fractions reflecting monoglycosides of delphinidin, cyanidin, petunidin and malvidin were obtained and all were shown to suppress the photooxidation of A2E at least in part by quenching singlet oxygen. The anthocyanins tested exhibited antioxidant activity of variable efficiency. The structural characteristics relevant to this variability likely included the ability to form a stable quinonoidal anhydro base at neutral pH, a conjugated diene structure in the C (pyrane) ring, the presence of hydroxyl groups on the B (benzene) ring and the relative hydrophobicity conferred by the arrangement of substituents on the B ring. Cells that had taken up anthocyanins also exhibited a resistance to the membrane permeabilization that occurs as a result of the detergent-like action of A2E. 相似文献
42.
Hasegawa JY Takata K Miyahara T Neya S Frisch MJ Nakatsuji H 《The journal of physical chemistry. A》2005,109(14):3187-3200
Excited states of free-base porphyrin isomers, porphycene (Pc), corrphycene (Cor), and hemiporphycene (hPc), were studied by the Symmetry-Adapted Cluster (SAC)/SAC-Configuration Interaction (CI) method. The absorption peaks of the porphyrin isomers were assigned on the basis of the SAC-CI spectra. The X, Y, X', and Y' bands of the porphyrin isomers, which have weak intensities, are identified. The differences in the Q-band absorptions among the isomers were clearly explained by the four-orbital model. In Cor and hPc, the wave function of the B-band corresponds to the mixture of the four-orbital excitations and the optically forbidden excitation of free-base porphin (P), due to the molecular symmetry lowering in the isomers. The B-band character is described by the five-orbital model in Pc and the six-orbital model in Cor and hPc. Two tetrazaporphycenes and two ring-extended (dibenzo) porphycenes were designed, and the Q-band transition moment was successfully controlled. These examples show that the control of the four-orbital energy levels is the guiding principle for pigment design in porphyrin compounds. 相似文献
43.
γ-Radiolysis of 5-fluorouracil and 5-fluorouridine derivatives having sulfur-containing substituents
Tokuyuki Kuroda Koji Hisamura Hiroshi Nishikawa Nobuhiro Nakamizo Yoshio Otsuji 《Journal of heterocyclic chemistry》1994,31(2):335-339
γ-Radiolysis reactions of eight 5-fluorouracil (5-FU) derivatives having sulfonyl group-containing substituents at the 1-position and five 5-fluorouridine (5-FUR) derivatives having thioureido group-containing substituents were studied under the conditions where hydrated electron (eaq?) and hydroxyl radical (HO·) become the principal reactive species. The 5-FU and 5-FUR derivatives were radiolyzed to give 5-FU and 5-FUR, respectively. The efficiency of the reactions depended upon the nature of reactive species and also upon the nature of substituents. The reactivity features of the γ-radiolysis reactions are discussed. 相似文献
44.
Research on phase relationships and structure studies by electron diffraction confirm VnO2n?1 (n = 3–9) phases between V2O3 and VO2. Metal-insulator phase transitions have been found in all phases but V3O5 and V7O13. Electrical, magnetic and thermodynamic properties associated with the transitions are reported for sintered samples or for single crystals prepared by a vapor-transport method. The results are collated and reviewed in summarized form. 相似文献
45.
By immersing Au substrate into a benzene solution containing both cobalt(II) phthalocyanine (CoPc) and copper(II) tetraphenyl-21H,23H-porphine (CuTPP), a two-dimensional alternate bimolecular structure was formed on the reconstructed Au(100)-(hex) surface. 相似文献
46.
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
47.
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
48.
Control of viscoelasticity using redox reaction 总被引:1,自引:0,他引:1
Tsuchiya K Orihara Y Kondo Y Yoshino N Ohkubo T Sakai H Abe M 《Journal of the American Chemical Society》2004,126(39):12282-12283
The viscoelasticity of a fluid was tuned with the Faradaic reaction of (11-ferrocenylundecyl)trimethylammonium bromide (FTMA), a "redox-switchable" surfactant. An aqueous solution of the reduced form of FTMA exhibited a remarkable viscoelasticity in the presence of sodium salicylate (NaSal) because of the formation of three-dimensional entanglement of wormlike micelles. Electrolytic oxidation of FTMA caused the viscosity of the system to dramatically decrease and the elasticity to disappear. This drastic decrease in viscoelasticity arose from the disruption of wormlike micelles. This novel electrorheological phenomenon is expected to be applicable to ink for inkjet printers, the electrochemically controlled release of substances entrapped in wormlike micelles of FTMA, and fluid flow rate control using electric signals. 相似文献
49.
Wakako Tsugawa Shuichi Horiuchi Mitsuharu Tanaka Hitoshi Wake Koji Sode 《Applied biochemistry and biotechnology》1996,56(3):301-310
A novel glucose dehydrogenase (GDH) from a marine bacteriumCytophaga marinoflava IFO 14170 was isolated from its membrane fraction. This GDH catalyzes the oxidation of a hydroxy group of glucose, but does
not react in its C-l position. This enzyme is composed of a single peptide with a mol wt of 67,000. The GDH can react under
high salinity. The optimum pH is around 8.0, showing a typical property of marine bacterial enzymes. Using this novel enzyme,
an enzymatic determination of 1,5-anhydro-D-glucitol (1,5AG) utilizing 2,6-dichrolophenolindophenol (DCIP) and phenazine methosulfate
(PMS) as electron mediators was caried out. A good linear correlation was observed from 0.5 mM to 4 mM of 1,5AG. 相似文献
50.
Bertosa B Kojić-Prodić B Wade RC Ramek M Piperaki S Tsantili-Kakoulidou A Tomić S 《Journal of chemical information and computer sciences》2003,43(5):1532-1541
The activity of a biological compound is dependent both on specific binding to a target receptor and its ADME (Absorption, Distribution, Metabolism, Excretion) properties. A challenge to predict biological activity is to consider both contributions simultaneously in deriving quantitative models. We present a novel approach to derive QSAR models combining similarity analysis of molecular interaction fields (MIFs) with prediction of logP and/or logD. This new classification method is applied to a set of about 100 compounds related to the auxin plant hormone. The classification based on similarity of their interaction fields is more successful for the indole than the phenoxy compounds. The classification of the phenoxy compounds is however improved by taking into account the influence of the logP and/or the logD values on biological activity. With the new combined method, the majority (8 out of 10) of the previously misclassified derivatives of phenoxy acetic acid are classified in accord with their bioassays. The recently determined crystal structure of the auxin-binding protein 1 (ABP1) enabled validation of our approach. The results of docking a few auxin related compounds with different biological activity to ABP1 correlate well with the classification based on similarity of MIFs only. Biological activity is, however, better predicted by a combined similarity of MIFs + logP/logD approach. 相似文献