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1.
Feng Cheng Shuqi Wu Wenwei Zheng Shengqun Su Takumi Nakanishi Wenhuang Xu Pritam Sadhukhan Hibiki Sejima Shimon Ikenaga Kaoru Yamamoto Kaige Gao Shinji Kanegawa Prof. Osamu Sato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(59):e202202161
The crystallization of a complex having electron transfer properties in a polar space group can induce the polarization switching of a crystal in a specific direction, which is attractive for the development of sensors, memory devices, and capacitors. Unfortunately, the probability of crystallization in a polar space group is usually low. Noticing that enantiopure compounds crystallize in Sohncke space groups, this paper reports a strategy for the molecular design of non-ferroelectric polarization switching crystals based on the use of intramolecular electron transfer and chirality. In addition, this paper describes the synthesis of a mononuclear valence tautomeric (VT) cobalt complex bearing an enantiopure ligand. The introduction of enantiomer enables the crystallization of the complex in the polar space group (P21). The polarization of the crystals along the b-axis direction is not canceled out and the VT transition is accompanied by a change in the macroscopic polarization of the polar crystal. Polarization switching via electron transfer is realized at around room temperature. 相似文献
2.
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
3.
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
4.
Kento Imanishi Benny Wahyudianto Dr. Tatsuhiro Kojima Dr. Nobuto Yoshinari Prof. Takumi Konno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(8):1827-1833
Here a unique single-crystal-to-single-crystal (SCSC) transformation of a 116-nuclear AuI72CdII40NaI4 cage-of-cage ( 2 CdNa) is reported, which was created from a trigold(I) metalloligand with d -penicillamine by way of a 9-nuclear AuI6CdII3 cage ( 1 ). Cage-of-cage 2 CdNa is composed of 12 cages of 1 that are linked by 4 Cd2+ and 4 Na+ ions, with its surface being covered by 12 NO3− ions to form a discrete, spherical molecule with a diameter ca. 4.7 nm. In crystal 2 CdNa, the cage-of-cage molecules are packed in a cubic lattice with a huge cell volume of ca. 4.5×105 Å3, so as to have large interstices with diameters of more than 3 nm. Upon soaking crystals 2 CdNa in aqueous Cu(NO3)2, all Cd2+ and Na+ were quickly exchanged by Cu2+ to produce an analogous AuI72CuII44 cage-of-cage ( 2 Cu) in a SCSC manner. Prolonged soaking led to the SCSC transformation to another supramolecular structure ( 2′ Cu) consisting of 152-nuclear AuI72CuII80 cage-of-cages that are alternately H-bonded with the AuI72CuII44 cage-of-cages. 2′ Cu showed the accommodation of MoO42− and the conversion of MoO42− to β-Mo8O264− in the crystal, with retention of single-crystallinity. 相似文献
5.
Prof. Dr. Masaki Shimizu Sho Nagano Takumi Kinoshita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(23):5162-5167
Fluorescence–phosphorescence dual-emissive compounds are valuable tools for ratiometric luminescence sensing. Herein, it is reported that 2,5-bis(phenylsulfonyl)- and 2,5-bis[bis(4-methoxyphenyl)phosphinyl]-1,4-disiloxybenzenes exhibit dual emission with emission peaks that were easily identified without performing time-gated measurement. The disiloxybenzenes in powder simultaneously fluoresced and phosphoresced at 358–374 and 457–470 nm, respectively, under vacuum. The intensity ratios of the phosphorescence/fluorescence maxima of the disiloxybenzenes in powder and in a thin film of poly(methyl methacrylate) were sensitive to temperature and molecular oxygen, respectively. The plots of the relative intensity versus temperature or partial pressure of molecular oxygen were well fitted with calibration curves defined by an exponential approximation with excellent correlation coefficients R2 (0.9708–0.9921), demonstrating the high potential of the disiloxybenzenes as precious metal-free probes applicable to ratiometric luminescence sensing. 相似文献
6.
Noriko Shimizu Tomoji Ozeki Hideyasu Shikama Tsuneji Sano Masahiro Sadakane 《Journal of Cluster Science》2014,25(3):755-770
We found that three isomers of mono-Ru substituted Keggin-type germanotungstate with a dmso ligand, [GeW11O39RuII(dmso)]6?, could be formed by a reaction of α-Keggin-type mono-lacunary germanotungstate, [α-GeW11O39]8?, with Ru(dmso)4Cl2. The main isomer is an α-isomer, and the others are β2-isomer and β3-isomer, which were confirmed by 1H NMR, cyclic voltammetry, IR, and single crystal X-ray structure analysis. 相似文献
7.
Ph. D. Satoru Takeshita Ph. D. Takumi Ono 《Angewandte Chemie (International ed. in English)》2023,62(41):e202306518
A new series of transparent aerogels of biopolymer-polysiloxane double networks is reported. Biopolymer aerogels have attracted much attention from green and sustainable aspects but suffered from strong hydrophilicity and difficulty to make homogeneous structures in nanoscale; these drawbacks are overcome by compositing with a polysiloxane network. Alginate-polymethylsilsesquioxane aerogel has high optical transparency, water repellency, comparable superinsulation property and improved bending flexibility compared to pure polymethylsilsesquioxane aerogel. The nanoscale homogeneity is realized by separating the crosslinking steps for two networks in a sequential protocol: condensation of siloxane bonds and metal-crosslinking of biopolymer. The crosslinking order, biopolymer-first or siloxane-first, and universality/limitation of biopolymer-crosslinker pairs are discussed to construct fundamental chemistry of double network systems for their further application potentials. 相似文献
8.
Takumi Nakajima Ken Takano Hiromu Maeda Dr. Yohei Ogiwara Prof. Dr. Norio Sakai 《化学:亚洲杂志》2021,16(24):4103-4107
The results of this study show that disilathiane is an effective mediator in the synthesis of alkyl aryl sulfides with disulfides and alkyl carboxylates. Mechanistic studies suggest that disilathiane promotes cleavage of the sulfur–sulfur bond of disulfides to generate thiosilane as a key intermediate. Diselenides were also applicable to this transformation to produce the corresponding selenides. 相似文献
9.
Peter J. Cumpson Naoko Sano Ian W. Fletcher Jose F. Portoles Mariela Bravo‐Sanchez Anders J. Barlow 《Surface and interface analysis : SIA》2015,47(10):986-993
Principal component analysis (PCA) and other multivariate analysis methods have been used increasingly to analyse and understand depth profiles in X‐ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and secondary ion mass spectrometry (SIMS). These methods have proved equally useful in fundamental studies as in applied work where speed of interpretation is very valuable. Until now these methods have been difficult to apply to very large datasets such as spectra associated with 2D images or 3D depth‐profiles. Existing algorithms for computing PCA matrices have been either too slow or demanded more memory than is available on desktop PCs. This often forces analysts to ‘bin’ spectra on much more coarse a grid than they would like, perhaps even to unity mass bins even though much higher resolution is available, or select only part of an image for PCA analysis, even though PCA of the full data would be preferred. We apply the new ‘random vectors’ method of singular value decomposition proposed by Halko and co‐authors to time‐of‐flight (ToF)SIMS data for the first time. This increases the speed of calculation by a factor of several hundred, making PCA of these datasets practical on desktop PCs for the first time. For large images or 3D depth profiles we have implemented a version of this algorithm which minimises memory needs, so that even datasets too large to store in memory can be processed into PCA results on an ordinary PC with a few gigabytes of memory in a few hours. We present results from ToFSIMS imaging of a citrate crystal and a basalt rock sample, the largest of which is 134GB in file size corresponding to 67 111 mass values at each of 512 × 512 pixels. This was processed into 100 PCA components in six hours on a conventional Windows desktop PC. © 2015 The Authors. Surface and Interface Analysis published by John Wiley & Sons Ltd. 相似文献
10.