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91.
Noriyuki Suzuki Kosuke Nishimura Nozomu Ohara Masayoshi Nishiura Yoshiro Masuyama 《Journal of organometallic chemistry》2012,696(26):4321-4326
The stereoisomerization of 2,5-disubstituted 1-zirconacyclopent-3-yne compounds, stable five-membered cycloalkynes, has been studied with regard to the mechanism. The bimetallic complex of 1,4-bis(trimethylsilyl)butatriene was synthesized and structurally characterized, although it seems unimportant for the stereoisomerization reactions. The isomerization of trans-1,1-bis(η5-cyclopentadienyl)-2,5-bis(trimethylsilyl)-1-zirconacyclopent-3-yne 2a into the cis-form in benzene-d6 solution were observed using 1H NMR spectroscopy at 50 °C in various concentrations. The reaction was first order with respect to trans-2a. This ruled out the possibility that a bimetallic complex was responsible for the isomerization. A kinetic isotope effect was observed (kH/kD = 1.8), suggesting that C–H activation is involved in the rate-determining step. A mechanism via hydrogen elimination from the complex of η4-π,π-coordination mode is proposed. 相似文献
92.
Kanno M Nakamura K Kanai E Hoki K Kono H Tanaka M 《The journal of physical chemistry. A》2012,116(9):2177-2183
There have been a growing number of articles that report dramatic improvements in the experimental performance of chemical reactions by microwave irradiation compared to that under conventional heating conditions. We theoretically examined whether nonthermal microwave effects on intramolecular reactions exist or not, in particular, on Newman-Kwart rearrangements and intramolecular Diels-Alder reactions. The reaction rates of the former calculated by the transition state theory, which consider only the thermal effects of microwaves, agree quantitatively with experimental data, and thus, the increases in reaction rates can be ascribed to dielectric heating of the solvent by microwaves. In contrast, for the latter, the temperature dependence of reaction rates can be explained qualitatively by thermal effects but the possibility of nonthermal effects still remains regardless of whether competitive processes are present or not. The effective intramolecular potential energy surface in the presence of a microwave field suggests that nonthermal effects arising from potential distortion are vanishingly small in intramolecular reactions. It is useful in the elucidation of the reaction mechanisms of microwave synthesis to apply the present theoretical approach with reference to the experiments where thermal and nonthermal effects are separated by screening microwave fields. 相似文献
93.
Summary: Here we show a new design concept of functional polymer gel for rapid deswelling by utilizing micelle‐forming ability of surfactant. A thermosensitive polymer bearing a surfactant was synthesized by using N‐isopropylacrylamide and a reactive surfactant. Above lower critical solution temperature, the grafted surfactant acts to form micelle structure. In the shrinking process, the inside water is rapidly squeezed out through hydrophilic channel between the formed micelles and consequently the gel shrinks quickly.
94.
Kawashima Natsumi Kitazaki Tomoya Nogo Kosuke Nishiyama Akira Wada Kenji Ishimaru Ichiro 《Optical Review》2020,27(6):530-541
Optical Review - We propose a superimposing interferogram method to enhance the sensitivity and interference definition of spatial-phase-shift interferometers. The proposed method uses a multi-slit... 相似文献
95.
The title pyridinium salts and pyridinium ylide-platinum(II) complexes have been reduced through a one-electron process at more positive potentials by 0.3 0.6 V than the corresponding ylides. Both the reduced pyridinium salts and Pt(II)-ylide complexes reacted with dioxygen, followed by elimination of the N-methylene and ylide protons to form pyridinium ylides and Pt(II)-pyridinium ylide complexes containing the three-coordinate ylide carbon atom, respectively. 相似文献
96.
Dr. Kosuke Ono Shunsuke Shimo Dr. Kohei Takahashi Dr. Nobuhiro Yasuda Dr. Hidehiro Uekusa Prof. Nobuharu Iwasawa 《Angewandte Chemie (International ed. in English)》2018,57(12):3113-3117
Dynamic interconversion between large covalent organic cages was achieved simply by heating or acid/base treatment. A mixture of the boroxine cages 12‐mer and 15‐mer was cleanly converted into a pyridine adduct of the 9‐mer boroxine cage upon treatment with pyridine, and the geometry of N‐coordinated boron atoms changed from trigonal to tetrahedral. The reverse reaction was achieved by heating or acid treatment. In this process, the larger boroxine cages 12‐mer and 15‐mer were found to be entropically favored owing to the release of free pyridine molecules from 9‐mer ?6 Py. 相似文献
97.
Utilization of Donor–Acceptor Interactions for the Catalytic Acceleration of Nucleophilic Additions to Aromatic Carbonyl Compounds 下载免费PDF全文
Tatsuhiro Uchikura Dr. Kosuke Ono Dr. Kohei Takahashi Prof. Nobuharu Iwasawa 《Angewandte Chemie (International ed. in English)》2018,57(8):2130-2133
A conceptually new method for the catalytic electrophilic activation of aromatic carbonyl substrates, by utilizing donor–acceptor interactions between an electron‐deficient macrocyclic boronic ester host ( [2+2] BTH‐F ) and an aromatic carbonyl guest substrate, was realized. In the presence of a catalytic amount of [2+2] BTH‐F , dramatic acceleration of the nucleophilic addition of a ketene silyl acetal towards either electron‐rich aromatic aldehydes or ketones was achieved. Several control experiments confirmed that inclusion of the aromatic substrates within [2+2] BTH‐F , through efficient donor–acceptor interactions, is essential for the acceleration of the reaction. 相似文献
98.
99.
Ryosuke NAKANISHI Kosuke TAKEUCHI Kazunori AKIZUKI Ryoma NAKAGOSHI Hironobu KAKIHANA 《Physical Therapy Research》2020,23(2):195
Objective: Neuromuscular electrical stimulation (NMES) has been noted as an effective pre- contraction for an increase of neural and muscle factors during twitch contractions. However, it is unknown if this intervention is effective for the rate of force development (RFD), which is the ability to increase joint torque strength as quickly as possible, during tetanic contractions. NMES can be safely used by anyone, but, the strength setting of NMES requires attention so as not to cause pain. Therefore, the purpose of this study investigated whether NMES at less painful levels was effective for RFD during tetanic contractions. We also investigated effect activation by analyzing electromyogram (EMG) and RFD for each phase. Methods: Eighteen healthy males were studied. Before and after NMES intervention at 10% or 20% maximal voluntary isometric contraction (MVIC) level (10%NMES, 20%NMES respectively), EMG activity and the initial phase (30-, 50-, 100-, and 200-msec) RFD were measured. Visual analog scale (VAS) was also measured as an indicator of pain during each NMES. Results: 20%NMES increased EMG activity and 30-, 50-, and 100-msec of RFD during MVIC, but could not improve 200 msec of RFD. However, 10%NMES could be failed to increase all phases RFD, but VAS was lower than that of 20% NMES. Conclusion: These results suggest that muscle pre-contraction using 20%NMES could induce moderate pain, but could be an effective intervention to improve RFD via neural factor activity. 相似文献
100.