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81.
Akira Katayama Takehiro Ohta Yuko Wasada‐Tsutsui Tomohiko Inomata Tomohiro Ozawa Takashi Ogura Hideki Masuda 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(33):11401-11406
Reported here is the N2 cleavage of a one‐electron oxidation reaction using trans‐[Mo(depe)2(N2)2] ( 1 ) (depe=Et2PCH2CH2PEt2), which is a classical molybdenum(0)‐dinitrogen complex supported by two bidentate phosphine ligands. The molybdenum(IV) terminal nitride complex [Mo(depe)2N][BArf4] ( 2 ) (BArf4=B(3,5‐(CF3)2C6H3)4) is synthesized by the one‐electron oxidation of 1 upon addition of a mild oxidant, [Cp2Fe][BArf4] (Cp=C5H5), and proceeds by N2 cleavage from a MoII‐N=N‐MoII structure. In addition, the electrochemical oxidation reaction for 1 also cleaved the N2 ligand to give 2 . The dimeric Mo complex with a bridging N2 is detected by in situ resonance Raman and in situ UV‐vis spectroscopies during the electrochemical oxidation reaction for 1 . Density‐functional theory (DFT) calculations reveal that the unstable monomeric oxidized MoI species is converted into 2 via the dimeric structure involving a zigzag transition state. 相似文献
82.
Introduction of carbohydrate auxiliary into enanine-based catalyst provided a novel enantiocontrol for aqueous aldol reaction. Methyl 2-(l-prolyl)amido-2-deoxy-α-d-glucopyranosides led to the enantiocontrol as parent amino acids did in the reaction of acetone with 4-nitrobenzaldehyde, and provided R-aldol in an improved efficiency compared with that of l-proline in aqueous media. The enantioreversal control of that with parent amino acid was observed in the reaction with methyl 2-(l-tert-leucyloxy)-α-d-glucopyranoside, which provided S-aldol predominantly in moderate efficiency. The novel enantiocontrol system was proposed to occur as a result of the generation of the transition state through the reaction of enamine with hydroxyl group on glucoside auxiliary. 相似文献
83.
We attempted to make an accurate depth profiling in secondary ion mass spectrometry (SIMS) including backside SIMS for ultra‐thin nanometer order layer. The depth profiles for HfO2 layers that were 3 and 5 nm thick in a‐Si/HfO2/Si were measured using quadrupole and magnetic sector type SIMS instruments. The depth profiling for an ultra‐thin layer with a high depth resolution strongly depends on how the crater‐edge and knock‐on effects can be properly reduced. Therefore, it is important to control the analyzing conditions, such as the primary ion energy, the beam focusing size, the incidence angle, the rastered area, and detected area to reduce these effects. The crater‐edge effect was significantly reduced by fabricating the sample into a mesa‐shaped structure using a photolithography technique. The knock‐on effect will be serious when the depth of the layer of interest from the surface is located within the depth of the ion mixing region due to the penetration of the primary ions. Finally, we were able to separately assign the origin of the distortion to the crater‐edge effect and knock‐on effect. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
84.
Tsutsui H Mochizuki T Maeda T Noge I Kitagawa Y Min JZ Todoroki K Inoue K Toyo'oka T 《Analytical and bioanalytical chemistry》2012,404(6-7):1925-1934
A simultaneous determination method for the enantiomers of chiral carboxylic acids by the combination of ultraperformance liquid chromatography and mass spectrometry (UPLC-MS/MS) has been developed. (S)(+)-1-(2-Pyrrolidinylmethyl)-pyrrolidine (S-PMP) was used as the derivatization reagent for the high-throughput determination of biological chiral carboxylic acids, i.e., lactic acid (LA) and 3-hydroxybutyric acid (HA). The S-PMP efficiently reacted with the carboxylic acids under mild conditions at room temperature in the presence of 2,2'-dipyridyl disulfide and triphenylphosphine. The resulting S-PMP derivatives were highly responsive in the electrospray ionization (ESI)-MS operating in the positive-ion mode and gave characteristic product ions during the MS/MS, which enabled the sensitive detection using selected reaction monitoring. The derivatization was effective for the enantiomeric separation of the chiral carboxylic acids, and the resolution values of DL-LA and DL-HA were 4.91 and 9.37, respectively. Furthermore, a rapid separation of the derivatives of DL-LA and DL-HA within 7?min was performed using the UPLC system. The limits of detection on the column were in the low femtogram range (5-12?fg). The proposed procedure was successfully applied for the determination of the D- and L-isomers of LA and HA in the saliva of diabetes mellitus (DM) patients and healthy volunteers. The D-LA in DM patients was clearly higher than that in normal subjects. The derivatization followed by UPLC-ESI-MS/MS enabled the enantiomeric separation and detection of trace amounts of LA and HA in human saliva with a simple pretreatment and small sample volume. 相似文献
85.
T Matsuno K Maruyama J Tsutsui 《Proceedings of the Japan Academy. Series B, Physical and biological sciences》2012,88(7):385-395
Following Part 1, a comparison of CO2 -emissions pathways between "zero-emissions stabilization (Z-stabilization)" and traditional stabilization is made under more realistic conditions that take into account the radiative forcings of other greenhouse gases and aerosols with the constraint that the temperature rise must not exceed 2 °C above the preindustrial level. It is shown that the findings in Part 1 on the merits of Z-stabilization hold under the more realistic conditions. The results clarify the scientific basis of the policy claim of 50% reduction of the world CO2 emissions by 2050. Since the highest greenhouse gas (GHG) concentration and temperature occur only temporarily in Z-stabilization pathways, we may slightly relax the upper limit of the temperature rise. We can then search for a scenario with larger emissions in the 21st century; such a scenario may have potential for practical application. It is suggested that in this Z-stabilization pathway, larger emissions in the near future may be important from a socioeconomic viewpoint.(Contributed by Taroh MATSUNO, M.J.A.). 相似文献
86.
Hiroshi Fukui Tomoo Katsura Takahiro Kuribayashi Takuya Matsuzaki Akira Yoneda Eiji Ito Yasuhiro Kudoh Satoshi Tsutsui Alfred Q. R. Baron 《Journal of synchrotron radiation》2008,15(6):618-623
Inelastic X‐ray scattering (IXS) measurements have been performed on an MgO single crystal in order to evaluate IXS as a methodology for accurate and precise determination of elastic constants and sound velocities. By performing the IXS experiment using a 12‐analyzer array, the complete set of single‐crystal elastic constants of MgO were determined to a precision better than 0.8% (sound velocities to better than 0.2%). The results are consistent with values in the literature. The precision and accuracy of this work, which is significantly better than other published work to date, demonstrates the potential of IXS in determining elastic properties. 相似文献
87.
Two theories of chiral fermions coupled to different quantum gravities in two dimensions are studied. One employs Jackiw's ansatz for classical gravity by introducing an auxiliary scalar, the other is based on the induced quantum gravity of Polyakov, which has no classical analogue. By investigating a localized theory of the effective action we show that in both cases a limited number of fermions of either chirality may couple consistently. It is stressed that the Weyl variable has to be quantized properly, which is related to recent work done on non-critical strings. 相似文献
88.
89.
Hiroaki Tsutsui Ryojiro Akashi 《Journal of polymer science. Part A, Polymer chemistry》2006,44(15):4644-4655
The effects of pigments contained in N‐isopropylacrylamide (NIPAM) gels on their volume‐change properties were investigated. All the NIPAM gel particles, containing various kinds and concentrations of pigments, showed a volume phase transition at 34 °C. No pigment affected the volume‐phase‐transition temperature of the NIPAM gels. As the concentration of the pigment in the NIPAM gels was increased, the amount of the volume change of the NIPAM gels was reduced. The water absorptivity of the NIPAM gels in the swollen state decreased as the pigment concentration increased, whereas the water absorptivity in the shrunken state was almost constant. Reducing the initial monomer concentration of the polymerization of the NIPAM gel increased the water absorptivity in the swollen state. With an increase in the water absorptivity, the volume changes of the NIPAM gels containing pigments were increased. Prototype light modulators in which the NIPAM gel particles containing pigment were dispersed between glass plates were fabricated. The light modulator using the gel particles with improved diameter change (d/d0 = 2.3, where d and d0 are the equilibrium diameter and the diameter of the fully shrunken state at 50 °C, respectively) exhibited a larger transmittance change from 8 to 79% than that using the gel particles before the improvement (d/d0 = 1.7; from 38 to 79%) according to temperature changes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4644–4655, 2006 相似文献
90.
A full account of stereoselective total synthesis of a novel glycolipid, acremomannolipin A (1), the potent calcium signal modulator isolated from Acremonium strictum, by employing the stereoselective β-mannosylation of 4,6-O-benzylidene-protected mannosyl sulfoxide with d-mannitol as the key reaction is described. The α-anomer (epi-1) of 1 was also synthesized selectively. The calcium modulating activity was reduced upon inversion of the configuration at the anomeric center, indicating that the β-configuration of the mannose moiety is preferable for the activity. 相似文献