Neutron diffraction evidence of microscopic charge inhomogeneities in the CuO2 plane of superconducting La2-xSrxCuO4 (0<or=x<or=0. 30)

High-resolution atomic pair distribution functions have been obtained using neutron powder diffraction data from La2-xSrxCuO4 over the range of doping 0相似文献   

Absence of residual quasiparticle conductivity in the underdoped cuprate YBa2Cu4O8

We report measurements of the in-plane thermal conductivity kappa of the stoichiometric underdoped cuprate YBa2Cu4O8 (Y124) below 1 K. kappa(T) is shown to follow a simple phononic T3 dependence at the lowest temperature T for both current directions, with a negligible linear quasiparticle contribution. This observation is in marked contrast with behavior reported in optimally doped cuprates, and implies that extended zero-energy (or low-energy) quasiparticles are absent in Y124.     

Synthesis,Crystal Structures,and Properties of 6,12‐Diaryl‐Substituted Indeno[1,2‐b]fluorenes

Fused polycyclic indeno[1,2‐b]fluorene derivatives with aryl substituents at the 6,12‐positions have been prepared as a potential antiaromatic 20π electronic system. They showed strong absorptions in the visible region and amphoteric redox properties. The quinoid‐type molecular structures were revealed by X‐ray crystal‐structure analysis, which indicated that the bond lengths of the quinoid unit depend on the aryl substituents. Whereas nucleus‐independent chemical shift NICS(1) calculations indicate the antiaromatic nature of the s‐indacene core, they have higher stability than substituted acene derivatives. The derivatives with difluorophenyl or anthryl groups were stable in solution. Vapor‐deposited thin films showed ambipolar carrier transportation in the field‐effect transistor devices.     

Efficient synthesis of 2,4-disubstituted 1,2,4-benzothiadiazin-3-one 1,1-dioxides on solid support

The first solid-phase synthesis of 1,2,4-benzothiadiazin-3-one 1,1-dioxides has been developed. Synthesis of the title compounds was achieved by the reduction of 2-nitrobenzenesulfonamides, followed by cyclization with carbonyldiimidazole. Because 1,2,4-benzothiadiazin-3-one 1,1-dioxides have been known to possess various bioactivities, this method is useful from the viewpoint of new drug discovery. In addition to the excellent purity of the title compounds, a large number of compounds can be synthesized with this method, because this synthesis includes four diversity points.     

Charge‐discharge properties of composites of polypyrrole and vanadium oxide powder

Composite of polypyrrole and crystalline V₂O₅ powder was prepared by chemical oxidation of pyrrole with use of V₂O₅ powder itself as an oxidizing agent. The V₂O₅ content was changed from 0 to 94 wt% by changing the amount of V₂O₅ dispersed in the preparation bath. The pellet electrodes could be prepared by pressing the composite powder alone even if amount of polypyrrole in the composite was only 6 wt%. The resulting pellet electrode exhibited good charge‐discharge performance as a positive electrode of Li rechargeable battery in an electrolyte solution as well as in a quasi‐solid cell fabricated by using a gel electrolyte sheet of poly(methyl methacrylate).     

Synthesis of nanometer-scale porphyrin wheels of variable size

Starting from 1,3-phenylene linked diporphyrin zinc(II) complex 2ZA, repeated stepwise Ag I-promoted coupling reactions provided linear oligomers from 2nZA up to 128ZA. Of these zigzag shaped porphyrin arrays, the Ag I-promoted intramolecular cyclization reaction of 2 nZA (n=5, 6, 8, 9, 12, and 16) under dilute conditions gave the corresponding cyclic porphyrin wheels C2nZA (n=5, 6, 8, 9, 12, and 16), whereas large arrays 2nZA (n=24, 32, and 48) did not provide cyclic porphyrin products. These large discrete porphyrin arrays and wheels were fully characterized by means of 1H NMR spectroscopy, MALDI-TOF mass spectrometry, UV/Vis absorption spectroscopy, GPC-HPLC analysis, and the scanning tunneling microscopy (STM) technique. The STM images of C12ZA and C18ZA reveal their large circular structures. In the cyclic structures of C2nZA in solution, however, the gradual decrease in fluorescence quantum yields and fluorescence lifetimes are observed, reflecting some conformational heterogeneities. Collectively, the present work provides an important contribution to the construction of fully covalently linked large cyclic arranged porphyrin arrays with ample electronic interactions as a model of light-harvesting antenna.     

Zinc chelation and photofluorochromic behavior of spironaphthoxazine intercalated into hydrophobically modified montmorillonite

Spironaphthoxazine (SNO) and Zn2+ were intercalated into montmorillonite interlayers hydrophobically modified by the alkyltrimethylammonium cation during UV light irradiation. The fluorescence spectra of the montmorillonite composites were observed to vary with an increase in the UV and visible light irradiation times. These composites exhibited two types of fluorescence emissions: F1, which originates from a new species, Xs, which is different from SNO (ring-closed form) and merocyanine (MC; ring-open form), and F2, which originates from the MC-Zn complex. With increasing UV light irradiation time, the F1 intensities decreased, whereas the F2 intensities increased. Xs, which is an intermediate species between SNO and MC, was transformed into MC and then coordinated with Zn2+ (i.e., MC-Zn complex) during the UV light irradiation. The reaction rate of the formation of the MC-Zn complex decreased for the hydrophobically modified montmorillonite due to a longer alkyl chain. The retrieval changes in the F1 and F2 intensities were observed with an increasing visible light irradiation time, implying the dissociation of the MC-Zn complex into Xs and Zn2+. The dissociation especially occurred for the hydrophobically modified montmorillonite with a longer alkyl chain. The formation and disappearance of Xs and the MC-Zn complex obeyed first-order kinetics, and therefore the interconversion between Xs and MC could be regarded as the rate-determining step of the whole reaction during the UV and visible light irradiations. The photoinduced reactions of the SNO species and Zn2+ were profoundly affected by the physicochemical environment provided by the clay interlayers. It is concluded that the present photoreactions can be controlled not only by the amounts of the intercalated SNO species and Zn2+, but also by the hydrophobic environment created by the surfactant molecules.     

A domino process for benzyne preparation: dual activation of o-(trimethylsilyl)phenols by nonafluorobutanesulfonyl fluoride

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.     

Comparison of luminescence ADP production assay and radiometric scintillation proximity assay for Cdc7 kinase

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.     

Efficient excited energy transfer reaction in clay/porphyrin complex toward an artificial light-harvesting system

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.