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91.
92.
Shin-ichi Matsuoka Shintaro ShimakawaKoji Takagi Masato Suzuki 《Tetrahedron letters》2011,52(50):6835-6838
The head-to-tail dimerization of methacrolein via the conjugate addition of methanol is catalyzed by various organic bases, such as an amine, phosphine, and N-heterocyclic carbene, to give 2,4-dimethyl-2-methoxymethylpentane-1,5-dial in moderate yields. Based on the interpretation of the key intermediates by electrospray ionization mass spectrometry, we propose a reaction mechanism involving the initial conjugate addition of the organic bases to methacrolein to generate a zwitterionic base followed by the activation of methanol. 相似文献
93.
Liu B Nakata K Sakai M Saito H Ochiai T Murakami T Takagi K Fujishima A 《Langmuir : the ACS journal of surfaces and colloids》2011,27(13):8500-8508
A facile new method that combines electrospray and hydrothermal treatment is used to prepare mesoporous core-shell TiO(2) spheres with high specific surface areas and high pore volumes. Interestingly, the resulting TiO(2) spheres are composed of anatase TiO(2) nanocrystals with exposed step-like {001} and smooth {010} facets. The percentage of exposed {001} facets can be adjusted by changing the experimental parameters used in the electrospray and hydrothermal treatment processes, such as the contents of poly(N-vinyl-2-pyrrolidone) and acetic acid. The combination of high specific surface area (>100 m(2) g(-1)), high pore volume (>0.30 cm(3) g(-1)), useful pore size (10-15 nm), spherical core-shell structure, and exposed high energy facets makes these TiO(2) spheres an important candidate for use in many photoelectrochemical applications. The formation mechanism of the mesoporous TiO(2) spheres is also studied. The great advantage of this method is that interesting and complicated mesoporous superstructures can be prepared using electrospray technology. 相似文献
94.
Doi T Shibata K Yoshida M Takagi M Tera M Nagasawa K Shin-ya K Takahashi T 《Organic & biomolecular chemistry》2011,9(2):387-393
Total synthesis of the (S)-stereoisomer of telomestatin (1) was accomplished. (S)-Telomestatin exhibited potency four times that of the natural product, (R)-telomestatin, which was the most potent telomerase inhibitor previously reported. In the circular dichroism spectral analysis of the complexes possessing randomly structured single-stranded d[TTAGGG](4) oligonucleotide, (S)-telomestatin, like (R)-telomestatin, induced an antiparallel G-quadruplex structure. The melting temperature (T(m)) value of the (S)-isomer complex was greater than that of the (R)-telomestatin complex. Therefore, it is concluded that the stereochemistry of the thiazoline of telomestatin is important to the binding ability of a G-quadruplex binder, and (S)-telomestatin as a G-quadruplex binder is more potent than the natural product. 相似文献
95.
Benzynes were generated from o-(trimethylsilyl)phenols using nonafluorobutanesulfonyl fluoride (NfF) by a domino process, i.e., the nonaflation of the phenolic hydroxyl group of o-(trimethylsilyl)phenols by NfF followed by the attack of the produced fluoride ion on the trimethylsilyl group. The generated benzyne immediately underwent various reactions to give polysubstituted benzenes. 相似文献
96.
Ishida Y Shimada T Masui D Tachibana H Inoue H Takagi S 《Journal of the American Chemical Society》2011,133(36):14280-14286
The quantitative excited energy transfer reaction between cationic porphyrins on an anionic clay surface was successfully achieved. The efficiency reached up to ca. 100% owing to the "Size-Matching Rule" as described in the text. It was revealed that the important factors for the efficient energy transfer reaction are (i) suppression of the self-quenching between adjacent dyes, and (ii) suppression of the segregated adsorption structure of two kinds of dyes on the clay surface. By examining many different kinds of porphyrins, we found that tetrakis(1-methylpyridinium-3-yl) porphyrin (m-TMPyP) and tetrakis(1-methylpyridinium-4-yl) porphyrin (p-TMPyP) are the suitable porphyrins to accomplish a quantitative energy transfer reaction. These findings indicate that the clay/porphyrin complexes are promising and prospective candidates to be used for construction of an efficient artificial light-harvesting system. 相似文献
97.
The spectral properties of two dicationic porphyrins, cis- and trans-bis(N-methylpyridinium-4-yl)diphenyl porphyrins, upon adsorption on clay mineral templates were investigated. A series of reduced charge Nanocor montmorillonites was used as host templates. The main impact was given on the influence of the layer charge on the absorption and fluorescence spectra. Adsorption of the porphyrins led to significant changes in their spectra but preserved the photoactivity of the dyes. The changes can be attributed to two phenomena: structural changes (flattening) of the porphyrin molecules and molecular aggregation. Latter one was more influenced by the molecular structure of the dyes and influenced the properties of mainly trans-isomer. The formation of the assemblies was significantly influenced by the layer charge of montmorillonite template. This study presents the example how one is able to influence the spectral properties and possibly also the functionality of adsorbed photoactive molecules via a strategy of appropriate combination of a photoactive component with specific inorganic templates. 相似文献
98.
Takagi T Shum D Parisi M Santos RE Radu C Calder P Rizvi Z Frattini MG Djaballah H 《Combinatorial chemistry & high throughput screening》2011,14(8):669-687
Several assay technologies have been successfully adapted and used in HTS to screen for protein kinase inhibitors; however, emerging comparative analysis studies report very low hit overlap between the different technologies, which challenges the working assumption that hit identification is not dependent on the assay method of choice. To help address this issue, we performed two screens on the cancer target, Cdc7-Dbf4 heterodimeric protein kinase, using a direct assay detection method measuring [(33)P]-phosphate incorporation into the substrate and an indirect method measuring residual ADP production using luminescence. We conducted the two screens under similar conditions, where in one, we measured [(33)P]-phosphate incorporation using scintillation proximity assay (SPA), and in the other, we detected luminescence signal of the ATP-dependent luciferase after regenerating ATP from residual ADP (LUM). Surprisingly, little or no correlation were observed between the positives identified by the two methods; at a threshold of 30% inhibition, 25 positives were identified in the LUM screen whereas the SPA screen only identified two positives, Tannic acid and Gentian violet, with Tannic acid being common to both. We tested 20 out of the 25 positive compounds in secondary confirmatory study and confirmed 12 compounds including Tannic acid as Cdc7-Dbf4 kinase inhibitors. Gentian violet, which was only positive in the SPA screen, inhibited luminescence detection and categorized as a false positive. This report demonstrates the strong impact in detection format on the success of a screening campaign and the importance of carefully designed confirmatory assays to eliminate those compounds that target the detection part of the assay. 相似文献
99.
Cimpoesu F Ito S Shimotani H Takagi H Dragoe N 《Physical chemistry chemical physics : PCCP》2011,13(20):9609-9615
Analysis of IR and Raman spectra of Ar@C(60) and Kr@C(60) shows that the incorporation of noble gas atoms causes a blue shift of low energy vibrations, which have radial character, and a red shift of higher energy ones which have a tangential character movement. The mechanism of these phenomena is explained on the basis of ab initio numerical experiments with DFT and MP2 procedures. Methodological discussions are advanced, altogether with a scheme for the estimation of the van der Waals interaction between fullerene and noble gas, based on the frequency shifts. 相似文献
100.
Minoru Tabata Nobuoki Eshima Ichiro Takagi 《Nonlinear Analysis: Real World Applications》2011,12(6):3261-3293
Urban and rural areas are formed by human migration from thinly populated areas to densely populated areas. It is known in sociodynamics that human migration is described by a nonlinear integro-partial differential equation whose unknown function denotes the population density. This equation is called the master equation. The master equation has its origin in statistical physics, and is regarded as one of the most fundamental equations in natural sciences, as its name suggests. We describe the formation of urban and rural areas by making use of global solutions of the mixed problem for this equation. In this paper we prove sufficient conditions for the mixed problem to have a unique global solution that converges to a two-tier step function as the time variable tends to infinity. This step function is a stationary solution of the master equation, and the higher (lower, respectively) step represents a stationary urban (rural, respectively) area. This result mathematically describes the formation of urban and rural areas in the real world. 相似文献