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1.
Dr. Manussada Ratanasak Takumi Murata Taishin Adachi Prof. Jun-ya Hasegawa Prof. Tadashi Ema 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(58):e202202210
BPh3 catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO2 and PhSiH3; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C6F5)3 shows little or no activity. 11B NMR spectra suggested the generation of [HBPh3]−. The detailed mechanism of the BPh3-catalyzed N-methylation of N-methylaniline ( 1 ) with CO2 and PhSiH3 was studied by using DFT calculations. BPh3 promotes the conversion of two substrates (N-methylaniline and CO2) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N+CO2−⋅⋅⋅BPh3]. The carbamate and BPh3 act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH3 to generate [HBPh3]−, which is used to produce key CO2-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh3]− species. 相似文献
2.
Takumi Watanabe Yuichiro Nishizawa Haruka Minato Dr. Chihong Song Prof. Dr. Kazuyoshi Murata Prof. Dr. Daisuke Suzuki 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):8934-8938
The three-dimensional structure of nanocomposite microgels was precisely determined by cryo-electron micrography. Several nanocomposite microgels that differ with respect to their nanocomposite structure, which were obtained from seeded emulsion polymerization in the presence of microgels, were used as model nanocomposite materials for cryo-electron micrography. The obtained three-dimensional segmentation images of these nanocomposite microgels provide important insights into the interactions between the hydrophobic monomers and the microgels, that is, hydrophobic styrene monomers recognize molecular-scale differences in polarity within the microgels during the emulsion polymerization. This result led to the formation of unprecedented multi-layered nanocomposite microgels, which promise substantial potential in colloidal applications. 相似文献
3.
Yoshiaki Murata Cheng-Huang Lin Totaro Imasaka 《Fresenius' Journal of Analytical Chemistry》1993,346(6-9):543-544
Summary A supersonic jet spectrum of 9,10-dichloroanthracene is measured by stimulated-emission-pumping fluorescence dip spectrometry and conventional fluorescence spectrometry. The performance obtained is compared for these spectrometric methods, providing same information concerned with the energy level of the ground state. The former is more preferential for measurement of a high-resolution spectrum, since the spectral resolution is determined by the linewidth of the dumping laser. On the other hand, the latter is more preferential for measurement with better sensitivity at the expense of the spectral resolution, since the fluorescence throughput can be improved by increasing the slit width of the monochromator.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday 相似文献
4.
Seiichi Nishizawa Tomoyuki Kamaishi Tomoyuki Yokobori Ryo Kato Ying-Yu Cui Takeshi Shioya Norio Teramae 《Analytical sciences》2004,20(11):1559-1565
Facilitated SO4(2-) transfers by hydrogen bond-forming ionophores are investigated across the nitrobenzene (NB)-water interface by using polarography with a dropping electrolyte electrode. Bis-thiourea 1, alpha,alpha'-bis(N'-p-nitrophenylthioureylene)-m-xylene, is found to significantly facilitate the transfer of the highly hydrophilic SO4(2-) whereas its counterpart, N-(p-nitrophenyl)-N'-propylthiourea (ionophore 2), cannot. In contrast to the predominant formation of a 1:1 complex with SO4(2-) in the bulk NB phase, the SO4(2-) transfer assisted by 1 is indeed based on the formation of a 1:2 complex between SO4(2-) and ionophore, even under the condition of [SO4(2-)]aq > [1]org. Such an exclusive formation of the 1:2 (SO4(2-) to ionophore) complex at the NB-water interface is not observed with structurally similar bis-thiourea 3, alpha,alpha'-bis(N'-phenylthioureylene)-m-xylene, where p-nitrophenyl moietes of bis-thiourea 1 are simply replaced by phenyl groups. The facilitated transfer of SO4(2-) with bis-thiourea 1 is further compared to that of HPO4(2-) and H2PO4- across the NB-water interface, which was previously shown to be assisted by 1 through the formation of the 1:1 and 2:1 (anion to ionophore) complexes, respectively. On the basis of these examinations, unique binding behaviors of hydrogen bond-forming ionophores at the NB-water interface are discussed, with a view towards development of ionophore-based anion-selective chemical sensors. 相似文献
5.
Aging of concrete buildings and determining the pH value on the surface of concrete by using a handy semi-conductive pH meter. 总被引:1,自引:0,他引:1
A new method was devised for measuring the pH of a concrete surface by pHBOY-P2 with a piece of filter paper by extracting the pH value from concrete. This is a simple and inexpensive method that does not damage the concrete building, and is easy to apply on concrete samples for monitoring. By using the method mentioned above, a drastic decrease of the pH value of concrete bridges and buildings has investigated. The method is environmentally friendly to detect the pH value change of concrete as an environmental sample investigation. 相似文献
6.
Yumi ShimadaMakoto Nakamura Toshimasa SuzukaJunji Matsui Ryo TatsumiKen Tsutsumi Tsumoru MorimotoHideo Kurosawa Kiyomi Kakiuchi 《Tetrahedron letters》2003,44(7):1401-1403
A new method for the construction of the AB-ring core of Taxol was developed utilizing a new skeletal transformation protocol as a pivotal step. The acid-catalyzed rearrangement of the cyclopentenone-allene photoadduct gave a bridged seven-membered ketone, which was easily transformed, using the intramolecular Suzuki reaction and the oxidative cleavage of the vicinal diol, to the bicyclic diketone. 相似文献
7.
XPS measurement revealed that the original state of TiO2 was changed to Ti2O3 and TiO by ion bombardment. TiO2 decreased and Ti2O3 increased at the initial stage. TiO increased at a later stage than Ti2O3. Each of them saturated after enough sputtering time.A formulation was proposed in order to explain the change of XPS spectra for oxides as a function of ion sputtering time. This formulation was based on reaction equations that contain two reduction processes (from TiO2 to Ti2O3 and from Ti2O3 to TiO), and sputtering effects. Using four fitting parameters (two reduction coefficients, sputtering yield and information depth), the present formula was fitted to the experimental results. The fitting results agree satisfactorily with the experimental results. The calculation shows that the reduction coefficient from TiO2 to Ti2O3 is about ten times larger than that from Ti2O3 to TiO. This calculation predicts that surface composition of an oxide that is changed by ion bombardment will reach a different value depending on its bulk composition. Moreover, the present formulation can determine the chemical states of compounds changed by ion bombardment. 相似文献
8.
9.
Ryo Nikkuni 《Mathematische Nachrichten》2007,280(8):897-906
Two spatial embeddings of a graph are said to be delta (resp. sharp) edge‐homotopic if they are transformed into each other by self delta (resp. sharp) moves and ambient isotopies. We show that any two spatial embeddings of a graph are delta (resp. sharp) edge‐homotopic if and only if the graph does not contain a subgraph which is homeomorphic to the theta graph or the disjoint union of two 1‐spheres, or equivalently G is homeomorphic to a bouquet. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
10.
Minoru Murata 《Journal of Functional Analysis》2002,194(1):53-141
We consider positive solutions of elliptic partial differential equations on non-compact domains of Riemannian manifolds. We explicitly determine Martin boundaries and Martin kernels for a class of elliptic equations in skew product form by exploiting and developing perturbation theory for elliptic equations and short/long-time estimates for fundamental solutions of parabolic equations. 相似文献