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31.
A Kunishita MZ Ertem Y Okubo T Tano H Sugimoto K Ohkubo N Fujieda S Fukuzumi CJ Cramer S Itoh 《Inorganic chemistry》2012,51(17):9465-9480
A mononuclear copper(II) superoxo species has been invoked as the key reactive intermediate in aliphatic substrate hydroxylation by copper monooxygenases such as peptidylglycine α-hydroxylating monooxygenase (PHM), dopamine β-monooxygenase (DβM), and tyramine β-monooxygenase (TβM). We have recently developed a mononuclear copper(II) end-on superoxo complex using a N-[2-(2-pyridyl)ethyl]-1,5-diazacyclooctane tridentate ligand, the structure of which is similar to the four-coordinate distorted tetrahedral geometry of the copper-dioxygen adduct found in the oxy-form of PHM (Prigge, S. T.; Eipper, B. A.; Mains, R. E.; Amzel, L. M. Science2004, 304, 864-867). In this study, structures and physicochemical properties as well as reactivity of the copper(I) and copper(II) complexes supported by a series of tridentate ligands having the same N-[2-(2-pyridyl)ethyl]-1,5-diazacyclooctane framework have been examined in detail to shed light on the chemistry dictated in the active sites of mononuclear copper monooxygenases. The ligand exhibits unique feature to stabilize the copper(I) complexes in a T-shape geometry and the copper(II) complexes in a distorted tetrahedral geometry. Low temperature oxygenation of the copper(I) complexes generated the mononuclear copper(II) end-on superoxo complexes, the structure and spin state of which have been further characterized by density functional theory (DFT) calculations. Detailed kinetic analysis on the O(2)-adduct formation reaction gave the kinetic and thermodynamic parameters providing mechanistic insights into the association and dissociation processes of O(2) to the copper complexes. The copper(II) end-on superoxo complex thus generated gradually decomposed to induce aliphatic ligand hydroxylation. Kinetic and DFT studies on the decomposition reaction have suggested that C-H bond abstraction occurs unimolecularly from the superoxo complex with subsequent rebound of the copper hydroperoxo species to generate the oxygenated product. The present results have indicated that a superoxo species having a four-coordinate distorted tetrahedral geometry could be reactive enough to induce the direct C-H bond activation of aliphatic substrates in the enzymatic systems. 相似文献
32.
Ohtsuka K Sato S Sato Y Sota K Ohzawa S Matsuda T Takemoto K Takamune N Juskowiak B Nagai T Takenaka S 《Chemical communications (Cambridge, England)》2012,48(39):4740-4742
When a biotinylated FRET probe based on a peptide-thrombin binding aptamer conjugate was introduced together with streptavidin and biotinylated nuclear export signal peptide into HeLa cells, the resulting ternary complex enabled visualization of K(+) concentration changes in the cell. 相似文献
33.
Dr. Masaru Kondo Dr. Shinobu Takizawa Yuzhao Jiang Prof. Dr. Hiroaki Sasai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(42):9866-9869
The Mills reaction and cyclization of readily available 2-aminobenzyl alcohols and nitrosobenzenes using thionyl bromide provided 2H-indazoles in up to 88 % yields. In the metal-free process, acetic acid played a crucial role for the both Mills reaction and cyclization. A brominated 2H-indazole could also be obtained through the one-pot sequence. 相似文献
34.
Naruyoshi Komiya Takeharu Kageyama Masaya Naito Takeshi Naota 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(5):503-505
rac‐Bis{μ‐trans‐2,2′‐[pentane‐1,5‐diylbis(azanediyl)]ditroponato}dipalladium(II), [Pd2(C19H20N2O2)2], has been synthesized and fully characterized using single‐crystal X‐ray diffraction, 1H NMR, FT–IR and mass spectroscopy. The trans coordination, vaulted structure and anti conformation have been unequivocally established from the X‐ray diffraction studies. This is the first example of a bis(aminotroponato)palladium complex. In the crystalline state, the molecule has twofold symmetry and each molecular unit undergoes intermolecular offset π‐stacking of the tropone rings to afford heterochiral interpenetrating dimers that are aligned in a lamellar manner with a herringbone packing motif. 相似文献
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36.
In order to examine basic properties of release from and through wax matrix layer, reservoir device matrix tablet was prepared from a physical mixture of hydrogenated caster oil and drug that was the same one in the reservoir. Release process could be divided into two stages. The first stage was the formation process of water channel by dissolving the drug in the wax matrix layer, and dissolved drug was released from the matrix layer following the square-root-of-time law equation. Hence, the drug penetration coefficient and tortuosity in the matrix layer were estimated. The second stage was the zero order release process of drug in the reservoir through the wax matrix layer. The release rate constant was calculated from the slope of line. Hence, the drug permeability coefficient and tortuosity were estimated. Fundamentally, tortuosity can not be expressed by some meaningful factors, and is obtained as an experimental result. By preparing wax matrix system from a physical mixture other than melted granule method, it was suggested that the matrix structure was uniform three-dimensionally. As a result, tortuosity could be expressed by a function of porosity, because unrecognized factors such as the surface coverage and thickness of melted wax on the soluble component should not be involved. 相似文献
37.
Tachi Y Aita K Teramae S Tani F Naruta Y Fukuzumi S Itoh S 《Inorganic chemistry》2004,43(15):4558-4560
A dicopper(I) complex supported by a novel asymmetric pentapyridine dinucleating ligand, consisting of tetradentate and tridentate metal-binding sites, has been synthesized and characterized. The dicopper(I) complex reacted with molecular oxygen at a low temperature to give an unprecedented mu-peroxo dicopper(II) complex presumably having a mu-eta1:eta2 binding mode, the spectroscopic features and the reactivity of which have been explored in detail. 相似文献
38.
Perovskite-type barium lithium fluoride (BaLiF3) was synthesized by pyrolysis of metal trifluoroacetates. The reaction temperature necessary for producing a single-phase material was found to be 600°C, which was lower than that for a conventional solid-state reaction or a melting method. Eu-doped BaLiF3 was also prepared and characterized to examine the suitability of trifluoroacetates for precursors in synthesizing homogeneous complex metal fluoride materials. It was demonstrated that trivalent Eu3+, which was used as acetate for a starting material, was reduced to divalent Eu2+ in the pyrolysis process of BaLiF3, as indicated by a broad blue emission due to an allowed 4f65d→4f7 transition at 408 nm with a ultraviolet excitation at 254 nm. The concentration quenching of the blue emission occurred at 5 at% of Eu in BaLiF3, indicating that Eu was homogeneously dispersed in the BaLiF3 host lattice. Mechanisms of the formation and reduction process of BaLiF3 were discussed based on pertinent chemical reactions. 相似文献
39.
Maki Sachiko Eiji Nishibori Shinobu Aoyagi Makoto Sakata Masaki Takata Mio Kondo Masaki Murata Ryota Sakamoto Hiroshi Nishihara 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(7):696-703
The title compound, [Fe2(C5H5)2(C40H22O2)] or 1,4‐(FcPh)2Aq [where FcPh is 2‐(4‐ferrocenylphenyl)ethynyl and Aq is anthraquinone], was synthesized in an attempt to obtain a new solvent‐incorporating porous material with a large void space. Thermodynamic data for 1,4‐(FcPh)2Aq show a phase transition at approximately 430 K. The crystal structure of solvent‐free 1,4‐(FcPh)2Aq was determined at temperatures of 90, 300 and 500 K using synchrotron powder diffraction data. A direct‐space method using a genetic algorithm was employed for structure solution. Charge densities calculated from observed structure factors by the maximum entropy method were employed for model improvement. The final models were obtained through multistage Rietveld refinements. In both phases, the structures of which differ only subtly, the planar Aq fragments are stacked alternately in opposite orientations, forming a one‐dimensional column. The FcPh arms lie between the stacks and fill the remaining space, leaving no voids. C—H...π interactions between the Ph and Fc fragments mediate crystal packing and stabilization. 相似文献
40.
Takaya Y Kikuchi H Terui Y Komiya J Furukawa KI Seya K Motomura S Ito A Oshima Y 《The Journal of organic chemistry》2000,65(4):985-989
For the elucidation of the diversity of secondary metabolites of Dictyostelium cellular slime molds, we investigate the constituent of three species of slime molds. From the methanol extract of their fruit bodies, we obtained three novel compounds, dictyopyrone A (1) and B (2) from D. discoideum and D. rhizoposium and dictyopyrone C (3) from D. longosporum. They possess a unique alpha-pyrone moiety with a side chain at the C-3 position. Their relative structures were elucidated by spectral means, and the absolute configuration was confirmed by asymmetric synthesis of 1. Since these compounds were obtained from different species of Dictyostelium slime molds, they may be a type of compound common to this genus. 相似文献