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  • 2010-2014  (78)
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Year
  • 1
    Publication Date: 2011-04-23
    Description: Amination of alkanes has generally required metal catalysts and/or high temperatures. Here we report that simple exposure of a broad range of alkanes to N-triflylimino-lambda(3)-bromane 1 at ambient temperature results in C-H insertion of the nitrogen functionality to afford triflyl-substituted amines in moderate to high yields. Marked selectivity for tertiary over secondary C-H bonds was observed; primary (methyl) C-H bonds were inert. Addition of hexafluoroisopropanol to inhibit decomposition of 1 dramatically improved the C-H amination efficiencies. Second-order kinetics, activation parameters (negative activation entropy), deuterium isotope effects, and theoretical calculations suggest a concerted asynchronous bimolecular transition state for the metal-free C-H amination event.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Ochiai, Masahito -- Miyamoto, Kazunori -- Kaneaki, Takao -- Hayashi, Satoko -- Nakanishi, Waro -- New York, N.Y. -- Science. 2011 Apr 22;332(6028):448-51. doi: 10.1126/science.1201686.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Graduate School of Pharmaceutical Sciences, University of Tokushima, 1-78 Shomachi, Tokushima 770-8505, Japan. mochiai@ph.tokushima-u.ac.jp〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/21512029" target="_blank"〉PubMed〈/a〉
    Keywords: Adamantane/chemistry ; Alkanes/*chemistry ; Amination ; Amines/*chemistry ; Bromobenzenes/*chemistry ; Carbon/chemistry ; Hydrocarbons, Brominated/*chemistry ; Hydrogen/chemistry ; Kinetics ; Physicochemical Processes ; Stereoisomerism ; Temperature ; Thermodynamics
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 2
    Publication Date: 2013-11-30
    Description: Transcription activator-like effector (TALE) nuclease (TALEN) is a site-specific nuclease, which can be freely designed and easily constructed. Numerous methods of constructing TALENs harboring different TALE scaffolds and repeat variants have recently been reported. However, the functionalities of structurally different TALENs have not yet been compared. Here, we report on the functional differences among several types of TALENs targeting the same loci. Using HEK293T cell-based single-strand annealing and Cel-I nuclease assays, we found that TALENs with periodically-patterned repeat variants harboring non-repeat-variable di-residue (non-RVD) variations (Platinum TALENs) showed higher activities than TALENs without non-RVD variations. Furthermore, the efficiencies of gene disruption mediated by Platinum TALENs in frogs and rats were significantly higher than in previous reports. This study therefore demonstrated an efficient system for the construction of these highly active Platinum TALENs (Platinum Gate system), which could establish a new standard in TALEN engineering. Scientific Reports 3 doi: 10.1038/srep03379
    Electronic ISSN: 2045-2322
    Topics: Natural Sciences in General
    Published by Springer Nature
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  • 3
    Publication Date: 2013-12-17
    Description: Author(s): R. Matysiak, P. Gegenwart, A. Ochiai, M. Antkowiak, G. Kamieniarz, and F. Steglich We report low-temperature specific heat, C(T), measurements on (Yb1−xLux)4As3, with x=0.01 and x=0.03, where nonmagnetic Lu atoms are randomly distributed on antiferromagnetic S=1/2 Heisenberg chains with J/kB=28 K. The observed reduction of C below 15 K with increasing x is accurately described by ... [Phys. Rev. B 88, 224414] Published Mon Dec 16, 2013
    Keywords: Magnetism
    Print ISSN: 1098-0121
    Electronic ISSN: 1095-3795
    Topics: Physics
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  • 4
    Publication Date: 2013-07-23
    Description: The recent applications of a TiO2-modified Ti-mesh filter (TMiP™) for water purification are summarized with newly collected data including biological assays as well as sewage water treatment. The water purification reactors consist of the combination of a TMiP, a UV lamp, an excimer VUV lamp, and an ozonation unit. The water purification abilities of the reactor were evaluated by decomposition of organic contaminants, inactivation of waterborne pathogens, and treatment efficiency for sewage water. The UV-C/TMiP/O3 reactor disinfected E. coli in aqueous suspension in approximately 1 min completely, and also decreased the number of E. coli in sewage water in 15 min dramatically. The observed rate constants of 7.5 L/min and 1.3 L/min were calculated by pseudo-first-order kinetic analysis respectively. Although organic substances in sewage water were supposed to prevent the UV-C/TMiP/O3 reactor from purifying water, the reactor reduced E. coli in sewage water continuously. On the other hand, although much higher efficiencies for decomposition of organic pollutants in water were achieved in the excimer/TMiP reactor, the disinfection activity of the reactor for waterborne pathogens was not as effective as the other reactors. The difference of efficiency between organic pollutants and waterborne pathogens in the excimer/TMiP reactor may be due to the size, the structure, and the decomposition mechanism of the organic pollutants and waterborne pathogens. These results show that a suitable system assisted by synergy of photocatalysts and other technologies such as ozonation has a huge potential as a practical wastewater purification system.
    Electronic ISSN: 2073-4441
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Published by MDPI Publishing
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  • 5
    Publication Date: 2013-09-01
    Description: Knowledge of the mechanisms of rain-induced shallow landslides can improve prediction of their occurrence and mitigate subsequent sediment disasters. Here, we examine an artificial slope's subsurface hydrology and propose a new slope stability analysis that includes seepage force and the down-slope transfer of excess shear forces. We measured pore water pressure and volumetric water content immediately prior to a shallow landslide on an artificial sandy slope of 32°: the direction of the subsurface flow shifted from downward to parallel to the slope in the deepest part of the landslide mass and this shift coincided with the start of soil displacement. A slope stability analysis that was restricted to individual segments of the landslide mass could not explain the initiation of the landslide; however, inclusion of the transfer of excess shear forces from up-slope to down-slope segments improved drastically the predictability. The improved stability analysis revealed that an unstable zone expanded down-slope with increase in soil water content, showing that the down-slope soil initially supported the unstable up-slope soil; destabilization of this down-slope soil was the eventual trigger of total slope collapse. Initially, the effect of apparent soil cohesion was the most important factor promoting slope stability, but seepage force became the most important factor promoting slope instability closer to the landslide occurrence. These findings indicate that seepage forces, controlled by changes in direction and magnitude of saturated and unsaturated subsurface flows, may be the main cause of shallow landslides in sandy slopes. This article is protected by copyright. All rights reserved.
    Print ISSN: 0885-6087
    Electronic ISSN: 1099-1085
    Topics: Architecture, Civil Engineering, Surveying , Geography
    Published by Wiley
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  • 6
    Publication Date: 2013-08-24
    Description: We have undertaken a detailed field, petrological, geochronological, and modeling study of Esan volcanic complex, northern Japan, in order to establish its eruptive history over the past 50,000 yr. The Esan volcanic complex includes seven lava domes, which are endogenous domes developed without basal edifices. Each dome was produced by intermediate to silicic magmas with 57–67 wt% SiO 2 that were erupted in magnitude 4–5 eruptions. Five explosively erupted pyroclastic units cover the aprons of these lava domes. The spatial and temporal relationships of the domes and the pyroclastic units have been determined in order to constrain the eruptive sequence of the Esan volcanic complex. A simple elastic model, assuming a hydraulic connection state, was utilized to study variations in long-term magma discharge at the Esan volcanic complex, which have been attributed to changes in magma storage conditions. The stepwise change in magma discharge with time, which is 4.2–5.3 x 10 4 m 3 /yr, is interpreted to reflect a change between magma chamber radius ( R c ) and magma depth ( H c ) caused by an upward migration of magma. Assuming a continuous input of magma from a deep source at a constant supply rate, the magma storage system that existed during the early stage of the Esan volcanic complex has been renewed, which will result in a shorter recurrence interval between eruptions rather than a long period of dormancy (22,400 yr). Given this finding, and the fact that the most recent eruption occurred 9000 yr ago, there is currently a risk of a large eruption at the Esan volcanic complex.
    Print ISSN: 0016-7606
    Electronic ISSN: 1943-2674
    Topics: Geosciences
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  • 7
    Publication Date: 2012-07-12
    Description: Langmuir DOI: 10.1021/la301126y
    Print ISSN: 0743-7463
    Electronic ISSN: 1520-5827
    Topics: Chemistry and Pharmacology
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  • 8
    Publication Date: 2012-05-03
    Description: This article reports our novel idea about the thermal stimulation of seabed hydrate reservoirs for the purpose of natural gas production. Our idea is to use submarine heat pumps, which are to be placed near the hydrate reservoir and work to recover thermal energy from the surrounding seawater and supply it into the reservoir. Although the heat pumps need an electricity supply from the sea surface level, they can provide thermal energy which is several times that of the consumed electricity in quantity. As a consequence, the use of submarine heat pumps has a distinct thermodynamic advantage over other thermal stimulation techniques already proposed in the literature.
    Electronic ISSN: 1996-1073
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Published by MDPI Publishing
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  • 9
    Publication Date: 2012-09-14
    Description: Photoresponsive fibers based on poly(acrylamide) (PAA) with methylene blue (MB) dye were prepared. All semicircular fibers show bending towards the direction of the flat surface of the fiber when illuminated. The fibers recover their initial shape when the illumination stops. The fiber is heated upon illumination and cooled to room temperature once the illumination is stopped. The fiber also is sensitive to humidity, showing bending behavior towards the direction of the flat surface of the fiber upon changing the humidity. The mechanical energy of the PAA/MB fiber is approximately 0.6 mN for the bending direction when it is illuminated. A possible mechanism for the bending behavior is as follow: (1) the fiber is heated upon illumination because of the photothermal effect, (2) the fiber loses water molecules, (3) the fiber shrinks; bending towards the direction of the flat surface of the fiber occurs because of a difference in the shrinkage for the flat surface and the other side of the fiber. Finally, we demonstrated that a PP ball (1.5 mg) can be moved by the mechanical energy produced by the changing shape of the fiber upon illumination.
    Print ISSN: 1110-662X
    Electronic ISSN: 1687-529X
    Topics: Electrical Engineering, Measurement and Control Technology , Energy, Environment Protection, Nuclear Power Engineering
    Published by Hindawi
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  • 10
    Publication Date: 2012-10-17
    Description: The Journal of Physical Chemistry B DOI: 10.1021/jp307998t
    Electronic ISSN: 1520-5207
    Topics: Chemistry and Pharmacology , Physics
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